Leuco colorants as bluing agents in laundry care compositions

ABSTRACT

A laundry care composition including: (a) at least one laundry care ingredient and (b) a leuco composition. The laundry care composition after 30 days of storage at 25° C. provides a whiteness benefit to cotton upon washing that is greater than the initial whiteness benefit. Methods of treating textiles with such laundry care compositions.

TECHNICAL FIELD

This application describes laundry care compositions that contain leucocolorants and their use in the laundering of textile articles. Thesetypes of colorants are provided in a stable, substantially colorlessstate and then may be transformed to an intense colored state uponexposure to certain physical or chemical changes such as, for example,exposure to oxygen, ion addition, exposure to light, and the like. Thelaundry care compositions containing the leuco colorants are designed toenhance the apparent or visually perceived whiteness of, or to impart adesired hue to, textile articles washed or otherwise treated with thelaundry care composition.

BACKGROUND

As textile substrates age, their color tends to fade or yellow due toexposure to light, air, soil, and natural degradation of the fibers thatcomprise the substrates. As such, to visually enhance these textilesubstrates and counteract the fading and yellowing the use of polymericcolorants for coloring consumer products has become well known in theprior art. For example, it is well known to use whitening agents, eitheroptical brighteners or bluing agents, in textile applications. However,traditional whitening agents tend to lose efficacy upon storage due todeleterious interactions with other formulation components (such as, forexample, perfumes). As such, formulators tend to increase the level ofwhitening agent used to counteract any efficacy lost upon storage.

Leuco dyes are also known in the prior art to exhibit a change from acolorless or slightly colored state to a colored state upon exposure tospecific chemical or physical triggers. The change in coloration thatoccurs is typically visually perceptible to the human eye. All existingcompounds have some absorbance in the visible light region (400-750 nm),and thus more or less have some color. In this invention, a dye isconsidered as a “leuco dye” if it did not render a significant color atits application concentration and conditions, but renders a significantcolor in its triggered form. The color change upon triggering stems fromthe change of the molar attenuation coefficient (also known as molarextinction coefficient, molar absorption coefficient, and/or molarabsorptivity in some literatures) of the leuco dye molecule in the400-750 nm range, preferably in the 500-650 nm range, and mostpreferably in the 530-620 nm range. The increase of the molarattenuation coefficient of a leuco dye before and after the triggeringshould be bigger than 50%, more preferably bigger than 200%, and mostpreferably bigger than 500%.

As such, there remains a need for an effective whitening agent thatincreases efficacy upon storage, rather than degrade and loose efficacy.

It has now surprisingly been found that the presently claimed leucocolorants not only provide the desired consumer whiteness benefit, butdetergents containing these colorants deliver increasing whiteness uponstorage. Therefore, the presently claimed laundry care compositionsactually become more effective the longer they are stored and eliminatethe need for formulators to add unnecessary and wasted levels ofwhitening agent to counteract the amount lost upon storage or tocompensate for loss of cleaning power over time due to the degradationof other cleaning components (such as enzymes, for example).

SUMMARY OF THE INVENTION

In one aspect, the present invention provides a laundry care compositioncomprising: (a) at least one laundry care ingredient and (b) a leucocomposition. The laundry care composition after 30 days of storage at25° C. provides a whiteness benefit to cotton upon washing that isgreater than the initial whiteness benefit.

The present invention further encompasses methods for treating textilearticles with a laundry care composition according to the presentinvention.

DETAILED DESCRIPTION Definitions

As used herein, the term “alkoxy” is intended to include C₁-C₈ alkoxyand alkoxy derivatives of polyols having repeating units such asbutylene oxide, glycidol oxide, ethylene oxide or propylene oxide.

As used herein, the interchangeable terms “alkyleneoxy” and“oxyalkylene,” and the interchangeable terms “polyalkyleneoxy” and“polyoxyalkylene,” generally refer to molecular structures containingone or more than one, respectively, of the following repeating units:—C₂H₄O—, —C₃H₆O—, —C₄H₈O—, and any combinations thereof. Non-limitingstructures corresponding to these groups include —CH₂CH₂O—,—CH₂CH₂CH₂O—, —CH₂CH₂CH₂CH₂O—, —CH₂CH(CH₃)O—, and —CH₂CH(CH₂CH₃)O—, forexample. Furthermore, the polyoxyalkylene constituent may be selectedfrom the group consisting of one or more monomers selected from a C₂₋₂₀alkyleneoxy group, a glycidyl group, or mixtures thereof.

The terms “ethylene oxide,” “propylene oxide” and “butylene oxide” maybe shown herein by their typical designation of “EO,” “PO” and “BO,”respectively.

As used herein, the terms “alkyl” and “alkyl capped” are intended tomean any univalent group formed by removing a hydrogen atom from asubstituted or unsubstituted hydrocarbon. Non-limiting examples includehydrocarbyl moieties which are branched or unbranched, substituted orunsubstituted including C₁-C₁₈ alkyl groups, and in one aspect, C₁-C₆alkyl groups.

As used herein, unless otherwise specified, the term “aryl” is intendedto include C₃-C₁₂ aryl groups. The term “aryl” refers to bothcarbocyclic and heterocyclic aryl groups.

As used herein, the term “alkaryl” refers to any alkyl-substituted arylsubstituents and aryl-substituted alkyl substituents. More specifically,the term is intended to refer to C₇₋₁₆ alkyl-substituted arylsubstituents and C₇₋₁₆ aryl substituted alkyl substituents which may ormay not comprise additional substituents.

As used herein, the term “detergent composition” is a sub-set of laundrycare composition and includes cleaning compositions including but notlimited to products for laundering fabrics. Such compositions may bepre-treatment composition for use prior to a washing step or may berinse added compositions, as well as cleaning auxiliaries, such asbleach additives and “stain-stick” or pre-treat types.

As used herein, the term “laundry care composition” includes, unlessotherwise indicated, granular, powder, liquid, gel, paste, unit dose,bar form and/or flake type washing agents and/or fabric treatmentcompositions, including but not limited to products for launderingfabrics, fabric softening compositions, fabric enhancing compositions,fabric freshening compositions, and other products for the care andmaintenance of fabrics, and combinations thereof. Such compositions maybe pre-treatment compositions for use prior to a washing step or may berinse added compositions, as well as cleaning auxiliaries, such asbleach additives and/or “stain-stick” or pre-treat compositions orsubstrate-laden products such as dryer added sheets.

As used herein, the term “leuco” (as used in reference to, for example,a compound, moiety, radical, dye, monomer, fragment, or polymer) refersto an entity (e.g., organic compound or portion thereof) that, uponexposure to specific chemical or physical triggers, undergoes one ormore chemical and/or physical changes that results in a shift from afirst color state (e.g., uncolored or substantially colorless) to asecond more highly colored state. Suitable chemical or physical triggersinclude, but are not limited to, oxidation, pH change, temperaturechange, and changes in electromagnetic radiation (e.g., light) exposure.Suitable chemical or physical changes that occur in the leuco entityinclude, but are not limited to, oxidation and non-oxidative changes,such as intramolecular cyclization. Thus, in one aspect, a suitableleuco entity can be a reversibly reduced form of a chromophore. In oneaspect, the leuco moiety preferably comprises at least a first and asecond π-system capable of being converted into a third combinedconjugated π-system incorporating said first and second π-systems uponexposure to one or more of the chemical and/or physical triggersdescribed above.

As used herein, the terms “leuco composition” or “leuco colorantcomposition” refers to a composition comprising at least two leucocompounds having independently selected structures as described infurther detail herein.

As used herein “average molecular weight” of the leuco colorant isreported as a weight average molecular weight, as determined by itsmolecular weight distribution: as a consequence of their manufacturingprocess, the leuco colorants disclosed herein may contain a distributionof repeating units in their polymeric moiety.

As used herein, the terms “maximum extinction coefficient” and “maximummolar extinction coefficient” are intended to describe the molarextinction coefficient at the wavelength of maximum absorption (alsoreferred to herein as the maximum wavelength), in the range of 400nanometers to 750 nanometers.

As used herein, the term “first color” is used to refer to the color ofthe laundry care composition before triggering, and is intended toinclude any color, including colorless and substantially colorless.

As used herein, the term “second color” is used to refer to the color ofthe laundry care composition after triggering, and is intended toinclude any color that is distinguishable, either through visualinspection or the use of analytical techniques such asspectrophotometric analysis, from the first color of the laundry carecomposition.

As used herein, the term “converting agent” refers to any oxidizingagent as known in the art other than molecular oxygen in any of itsknown forms (singlet and triplet states).

As used herein, the term “triggering agent” refers to a reactantsuitable for converting the leuco composition from a colorless orsubstantially colorless state to a colored state.

As used herein, the term “whitening agent” refers to a dye or a leucocolorant that may form a dye once triggered that when on white cottonprovides a hue to the cloth with a relative hue angle of 210 to 345, oreven a relative hue angle of 240 to 320, or even a relative hue angle of250 to 300 (e.g., 250 to 290).

As used herein, “cellulosic substrates” are intended to include anysubstrate which comprises at least a majority by weight of cellulose.Cellulose may be found in wood, cotton, linen, jute, and hemp.Cellulosic substrates may be in the form of powders, fibers, pulp andarticles formed from powders, fibers and pulp. Cellulosic fibers,include, without limitation, cotton, rayon (regenerated cellulose),acetate (cellulose acetate), triacetate (cellulose triacetate), andmixtures thereof. Articles formed from cellulosic fibers include textilearticles such as fabrics. Articles formed from pulp include paper.

As used herein, articles such as “a” and “an” when used in a claim, areunderstood to mean one or more of what is claimed or described.

As used herein, the terms “include/s” and “including” are meant to benon-limiting.

As used herein, the term “solid” includes granular, powder, bar andtablet product forms.

As used herein, the term “fluid” includes liquid, gel, paste and gasproduct forms.

The test methods disclosed in the Test Methods Section of the presentapplication should be used to determine the respective values of theparameters of Applicants' inventions.

Unless otherwise noted, all component or composition levels are inreference to the active portion of that component or composition, andare exclusive of impurities, for example, residual solvents orby-products, which may be present in commercially available sources ofsuch components or compositions.

All percentages and ratios are calculated by weight unless otherwiseindicated. All percentages and ratios are calculated based on the totalcomposition unless otherwise indicated.

In one aspect, the molar extinction coefficient of said second coloredstate at the maximum absorbance in the wavelength in the range 200 to1,000 nm (more preferably 400 to 750 nm) is preferably at least fivetimes, more preferably 10 times, even more preferably 25 times, mostpreferably at least 50 times the molar extinction coefficient of saidfirst color state at the wavelength of the maximum absorbance of thesecond colored state. Preferably, the molar extinction coefficient ofsaid second colored state at the maximum absorbance in the wavelength inthe range 200 to 1,000 nm (more preferably 400 to 750 nm) is at leastfive times, preferably 10 times, even more preferably 25 times, mostpreferably at least 50 times the maximum molar extinction coefficient ofsaid first color state in the corresponding wavelength range. Anordinarily skilled artisan will realize that these ratios may be muchhigher. For example, the first color state may have a maximum molarextinction coefficient in the wavelength range from 400 to 750 nm of aslittle as 10 M⁻¹cm⁻¹, and the second colored state may have a maximummolar extinction coefficient in the wavelength range from 400 to 750 nmof as much as 80,000 M⁻¹cm⁻¹ or more, in which case the ratio of theextinction coefficients would be 8,000:1 or more.

In one aspect, the maximum molar extinction coefficient of said firstcolor state at a wavelength in the range 400 to 750 nm is less than 1000M⁻¹cm⁻¹, and the maximum molar extinction coefficient of said secondcolored state at a wavelength in the range 400 to 750 nm is more than5,000 M⁻¹cm⁻¹, preferably more than 10,000, 25,000, 50,000 or even100,000 M⁻¹cm⁻¹. A skilled artisan will recognize and appreciate that apolymer comprising more than one leuco moiety may have a significantlyhigher maximum molar extinction coefficient in the first color state(e.g., due to the additive effect of a multiplicity of leuco moieties orthe presence of one or more leuco moieties converted to the secondcolored state). Where more than one leuco moiety is attached to amolecule, the maximum molar extinction coefficient of said second colorstate may be more than n×ε where n is the number of leuco moieties plusoxidized leuco moieties present on the molecule, and ε is selected from5,000 M⁻¹cm⁻¹, preferably more than 10,000, 25,000, 50,000 or even100,000 M⁻¹cm⁻¹. Thus for a molecule that has two leuco moieties, themaximum molar extinction coefficient of said second color state may bemore than 10,000 M⁻¹cm⁻¹, preferably more than 20,000, 50,000, 100,000or even 200,000 M⁻¹cm⁻¹. While n could theoretically be any integer, oneskilled in the art appreciates that n will typically be from 1 to 100,more preferably 1 to 50, 1 to 25, 1 to 10 or even 1 to 5.

The amount of leuco colorant used in the laundry care compositions ofthe present invention may be any level suitable to achieve the aims ofthe invention. In one aspect, the laundry care composition comprisesleuco colorant in an amount from about 0.0001 wt % to about 1.0 wt %,preferably from 0.0005 wt % to about 0.5 wt %, even more preferably fromabout 0.0008 wt % to about 0.2 wt %, most preferably from 0.004 wt % toabout 0.1 wt %.

In another aspect, the laundry care composition comprises leuco colorantin an amount from 0.0025 to 5.0 milliequivalents/kg, preferably from0.005 to 2.5 milliequivalents/kg, even more preferably from 0.01 to 1.0milliequivalents/kg, most preferably from 0.05 to 0.50milliequivalents/kg, wherein the units of milliequivalents/kg refer tothe milliequivalents of leuco moiety per kg of the laundry composition.For leuco colorants comprising more than one leuco moiety, the number ofmilliequivalents is related to the number of millimoles of the leucocolorant by the following equation: (millimoles of leuco colorant)×(no.of milliequivalents of leuco moiety/millimole of leucocolorant)=milliequivalents of leuco moiety. In instances where there isonly a single leuco moiety per leuco colorant, the number ofmilliequivalents/kg will be equal to the number of millimoles of leucocolorant/kg of the laundry care composition.

The present invention relates to a class of leuco colorants that may beuseful for use in laundry care compositions, such as liquid laundrydetergent, to provide a hue to whiten textile substrates. Leucocolorants are compounds that are essentially colorless or only lightlycolored but are capable of developing an intense color upon activation.One advantage of using leuco compounds in laundry care compositions isthat such compounds, being colorless until activated, allow the laundrycare composition to exhibit its own color. The leuco colorant generallydoes not alter the primary color of the laundry care composition. Thus,manufacturers of such compositions can formulate a color that is mostattractive to consumers without concern for added ingredients, such asbluing agents, affecting the final color value of the composition.

The range of textile articles encountered in the consumer home is quitelarge and often comprises garments constructed from a wide variety ofboth natural and synthetic fibers, as well as mixtures of these eitherin the same wash load or even in the same garment. The articles can beconstructed in a variety of ways and may comprise any of a vast array offinishes that may be applied by the manufacturer. The amount of any suchfinish remaining on a consumer's textile article depends on a wide arrayof factors among which are the durability of the finish under theparticular washing conditions employed by the consumer, the particulardetergents and additives the consumer may have used as well as thenumber of cycles that the article has been washed. Depending on thehistory of each article, finishes may be present to varying degrees oressentially absent, while other materials present in the wash or rinsecycles and contaminants encountered during wearing may start toaccumulate on the article.

The skilled artisan is keenly aware that any detergent formulation usedby consumers will encounter textile articles that represent the fullrange of possibilities and expects that there not only may be, but infact will be, significant differences in the way the formulationperforms on some textiles articles as opposed to others. Thesedifferences can be found through routine experimentation. For example,the leuco colorants of the present invention have been found to increasethe whiteness of consumer aged garments and also garments to whichfabric enhancers have been applied, more than they increase thewhiteness of new garments from which the finishes have been removed withsuccessive washes. Thus formulations comprising such leuco colorants maybe preferred over traditional formulations, even formulations containingconventional hueing agents, since newer garments typically have less ofa yellowing issue whereas older consumer aged garments are more prone tohave an issue with yellowing. The leuco colorants of the instantinvention have a bias for increasing the whiteness of aged garments overclean new garments that is larger than the bias displayed by manytraditional hueing agents.

In one aspect, the invention relates to a leuco composition selectedfrom the group consisting of a diarylmethane leuco, a triarylmethaneleuco, an oxazine leuco, a thiazine leuco, a hydroquinone leuco, anarylaminophenol leuco and mixtures thereof.

Suitable diarylmethane leuco compounds for use herein include, but arenot limited to, diarylmethylene derivatives capable of forming a secondcolored state as described herein. Suitable examples include, but arenot limited to, Michler's methane, a diarylmethylene substituted with an—OH group (e.g., Michler's hydrol) and ethers and esters thereof, adiarylmethylene substituted with a photocleavable moiety, such as a —CNgroup (bis(para-N,N-dimethyl)phenyl)acetonitrile), and similar suchcompounds.

In one aspect, the invention relates to a composition comprising one ormore leuco compounds conforming to the group selected from:

(f) mixtures thereof;

wherein the ratio of Formula I-V to its oxidized form is at least 1:19,1:9, or 1:3, preferably at least 1:1, more preferably at least 3:1, mostpreferably at least 9:1 or even 19:1.

In the structure of Formula (I), wherein each individual R_(o), R_(m)and R_(p) group on each of rings A, B and C is independently selectedfrom the group consisting of hydrogen, deuterium and R⁵; each R⁵ isindependently selected from the group consisting of halogens, nitro,alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substitutedalkaryl, —(CH₂)_(n)—O—R¹, —(CH₂)_(n)—NR¹R², —C(O)R¹, —C(O)OR¹, —C(O)O⁻,—C(O)NR¹R², —OC(O)R¹, —OC(O)OR¹, —OC(O)NR¹R², —S(O)₂R¹, —S(O)₂OR¹,—S(O)₂O⁻, —S(O)₂NR¹R², —NR¹C(O)R², —NR¹C(O)OR², —NR¹C(O)SR²,—NR¹C(O)NR²R³, —P(O)₂R¹, —P(O)(OR¹)₂, —P(O)(OR¹)O⁻, and —P(O)(O⁻)₂,wherein the index n is an integer from 0 to 4, preferably from 0 to 1,most preferably 0; wherein two R_(o) on different A, B and C rings maycombine to form a fused ring of five or more members; when the fusedring is six or more members, two R_(o) on different A, B and C rings maycombine to form an organic linker optionally containing one or moreheteroatoms; in one embodiment two R_(o) on different A, B and C ringscombine to form a heteroatom bridge selected from —O— and —S— creating asix member fused ring; an R_(o) and R_(m) on the same ring or an R_(m)and R_(p) on the same ring may combine to form a fused aliphatic ring orfused aromatic ring either of which may contain heteroatoms; on at leastone of the three rings A, B or C, preferably at least two, morepreferably at least three, most preferably all four of the R_(o) andR_(m) groups are hydrogen, preferably all four R_(o) and R_(m) groups onat least two of the rings A, B and C are hydrogen; in some embodiments,all R_(o) and R_(m) groups on rings A, B and C are hydrogen; preferablyeach R_(p) is independently selected from hydrogen, —OR¹ and —NR¹R²; nomore than two, preferably no more than one of R_(p) is hydrogen,preferably none are hydrogen; more preferably at least one, preferablytwo, most preferably all three R_(p) are —NR¹R²; in some embodiments,one or even two of the Rings A, B and C may be replaced with anindependently selected C₃-C₉ heteroaryl ring comprising one or twoheteroatoms independently selected from O, S and N, optionallysubstituted with one or more independently selected R⁵ groups; G isindependently selected from the group consisting of hydrogen, deuterium,C₁-C₁₆ alkoxide, phenoxide, bisphenoxide, nitrite, nitrile, alkyl amine,imidazole, arylamine, polyalkylene oxide, halides, alkylsulfide, arylsulfide, or phosphine oxide; in one aspect the fraction[(deuterium)/(deuterium+hydrogen)] for G is at least 0.20, preferably atleast 0.40, even more preferably at least 0.50 and most preferably atleast 0.60 or even at least 0.80; wherein any two of R¹, R² and R³attached to the same heteroatom can combine to form a ring of five ormore members optionally comprising one or more additional heteroatomsselected from the group consisting of —O—, —NR¹⁵—, and —S—.In the structure of Formula (II)-(III), e and f are independentlyintegers from 0 to 4; each R²⁰ and R²¹ is independently selected fromthe group consisting of halogens, a nitro group, alkyl groups,substituted alkyl groups, —NC(O)OR¹, —NC(O)SR¹, —OR¹, and —NR¹R²; eachR²⁵ is independently selected from the group consisting ofmonosaccharide moiety, disaccharide moiety, oligosaccharide moiety, andpolysaccharide moiety, —C(O)R¹, —C(O)OR¹, —C(O)NR¹R²; each R²² and R²³is independently selected from the group consisting of hydrogen, alkylgroups, and substituted alkyl groups.In the structure of Formula (IV), R³⁰ is positioned ortho or para to thebridging amine moiety and is selected from the group consisting of —OR³⁸and —NR³⁶R³⁷, each R³⁶ and R³⁷ is independently selected from the groupconsisting of hydrogen, alkyl groups, substituted alkyl groups, arylgroups, substituted aryl groups, acyl groups, R⁴, —C(O)OR¹, —C(O)R¹, and—C(O)NR¹R²; R³⁸ is selected from the group consisting of hydrogen, acylgroups, —C(O)OR¹, —C(O)R¹, and —C(O)NR¹R²; g and h are independentlyintegers from 0 to 4; each R³¹ and R³² is independently selected fromthe group consisting of alkyl groups, substituted alkyl groups, arylgroups, substituted aryl groups, alkaryl, substituted alkaryl,—(CH₂)_(n)—O—R¹, —(CH₂)_(n)—NR¹R², —C(O)R¹, —C(O)OR¹, —C(O)O⁻,—C(O)NR¹R², —OC(O)R¹, —OC(O)OR¹, —OC(O)NR¹R², —S(O)₂R¹, —S(O)₂OR¹,—S(O)₂O⁻, —S(O)₂NR¹R², —NR¹C(O)R², —NR¹C(O)OR², —NR¹C(O)SR²,—NR¹C(O)NR²R³, —P(O)₂R¹, —P(O)(OR¹)₂, —P(O)(OR¹)O⁻, and —P(O)(O⁻)₂,wherein the index n is an integer from 0 to 4, preferably from 0 to 1,most preferably 0; —NR³⁴R³⁵ is positioned ortho or para to the bridgingamine moiety and R³⁴ and R³⁵ are independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, aryl, substitutedaryl, alkaryl, substituted alkaryl, and R⁴; R³³ is independentlyselected from the group consisting of hydrogen, —S(O)₂R¹, —C(O)N(H)R¹;—C(O)OR¹; and —C(O)R¹; when g is 2 to 4, any two adjacent R³¹ groups maycombine to form a fused ring of five or more members wherein no morethan two of the atoms in the fused ring may be nitrogen atoms;In the structure of Formula (V), X⁴⁰ is selected from the groupconsisting of an oxygen atom, a sulfur atom, and NR⁴⁵; R⁴⁵ isindependently selected from the group consisting of hydrogen, deuterium,alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substitutedalkaryl, —S(O)₂OH, —S(O)₂O⁻; —C(O)OR¹, —C(O)R¹, and —C(O)NR¹R²; R⁴⁰ andR⁴¹ are independently selected from the group consisting of—(CH₂)_(n)—O—R¹, —(CH₂)_(n)—NR¹R³, wherein the index n is an integerfrom 0 to 4, preferably from 0 to 1, most preferably 0; j and k areindependently integers from 0 to 3; R⁴² and R⁴³ are independentlyselected from the group consisting of alkyl, substituted alkyl, aryl,substituted aryl, alkaryl, substituted alkaryl, —S(O)₂R¹, —C(O)NR¹R²,—NC(O)OR¹, —NC(O)SR¹, —C(O)OR¹, —C(O)R¹, —(CH₂)_(n)—O—R¹,—(CH₂)_(n)—NR¹R², wherein the index n is an integer from 0 to 4,preferably from 0 to 1, most preferably 0; R⁴⁴ is —C(O)R¹, —C(O)NR¹R²,and —C(O)OR¹;In the structures of Formula (I)-(V), wherein any charge present in anyof the preceeding groups is balanced with a suitable independentlyselected internal or external counterion. Suitable independentlyselected external counterions may be cationic or anionic. Examples ofsuitable cations include but are not limited to one or more metalspreferably selected from Group I and Group II, the most preferred ofthese being Na, K, Mg, and Ca, or an organic cation such as iminium,ammonium, and phosphonium. Examples of suitable anions include but arenot limited to: fluoride, chloride, bromide, iodide, perchlorate,hydrogen sulfate, sulfate, aminosulfate, nitrate, dihydrogen phosphate,hydrogen phosphate, phosphate, bicarbonate, carbonate, methosulfate,ethosulfate, cyanate, thiocyanate, tetrachlorozincate, borate,tetrafluoroborate, acetate, chloroacetate, cyanoacetate, hydroxyacetate,aminoacetate, methylaminoacetate, di- and tri-chloroacetate,2-chloro-propionate, 2-hydroxypropionate, glycolate, thioglycolate,thioacetate, phenoxyacetate, trimethylacetate, valerate, palmitate,acrylate, oxalate, malonate, crotonate, succinate, citrate,methylene-bis-thioglycolate, ethylene-bis-iminoacetate,nitrilotriacetate, fumarate, maleate, benzoate, methylbenzoate,chlorobenzoate, dichlorobenzoate, hydroxybenzoate, aminobenzoate,phthalate, terephthalate, indolylacetate, chlorobenzenesulfonate,benzene sulfonate, toluenesulfonate, biphenyl-sulfonate andchlorotoluenesulfonate. Those of ordinary skill in the art are wellaware of different counterions which can be used in place of thoselisted above.In the structures of Formula (I)-(V), R¹, R², R³, and R¹⁵ areindependently selected from the group consisting of hydrogen, alkyl,substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl,and R⁴; wherein R⁴ is a organic group composed of one or more organicmonomers with said monomer molecular weights ranging from 28 to 500,preferably 43 to 350, even more preferably 43 to 250, wherein theorganic group may be substituted with one or more additional leucocolorant moieties conforming to the structure of Formula I-V. In oneaspect, R⁴ is selected from the group consisting of alkyleneoxy(polyether), oxoalkyleneoxy (polyesters), oxoalkyleneamine (polyamides),epichlorohydrin, quaternized epichlorohydrin, alkyleneamine,hydroxyalkylene, acyloxyalkylene, carboxyalkylene, carboalkoxyalkylene,and sugar. Where any leuco colorant comprises an R⁴ group with three ormore contiguous monomers, that leuco colorant is defined herein as a“polymeric leuco colorant”. One skilled in the art knows that theproperties of a compound with regard to any of a number ofcharacteristic attributes such as solubility, partitioning, deposition,removal, staining, etc., are related to the placement, identity andnumber of such contiguous monomers incorporated therein. The skilledartisan can therefore adjust the placement, identity and number of suchcontiguous monomers to alter any particular attribute in a more or lesspredictable fashion.

The leuco compounds described above are believed to be suitable for usein the treatment of textile materials, such as in domestic launderingprocesses. In particular, it is believed that the leuco compounds willdeposit onto the fibers of the textile material due to the nature of theleuco compound. Further, once deposited onto the textile material, theleuco compound can be converted to a colored compound through theapplication of the appropriate chemical or physical triggers that willconvert the leuco compound to its colored form. For example, the leucocompound can be converted to its colored form upon oxidation of theleuco compound to the oxidized compound. By selecting the proper leucomoiety, the leuco compound can be designed to impart a desired hue tothe textile material as the leuco compound is converted to its coloredform. For example, a leuco compound that exhibits a blue hue uponconversion to its colored form can be used to counteract the yellowingof the textile material to normally occurs due to the passage of timeand/or repeated launderings. Thus, in other embodiments, the inventionprovides laundry care compositions comprising the above-described leucocompound and domestic methods for treating a textile material (e.g.,methods for washing an article of laundry or clothing).

Preferably the leuco compound gives a hue to the cloth with a relativehue angle of 210 to 345, or even a relative hue angle of 240 to 320, oreven a relative hue angle of 250 to 300 (e.g., 250 to 290). The relativehue angle can be determined by any suitable method as known in the art.However, preferably it may be determined as described in further detailherein with respect to deposition of the leuco entity on cotton relativeto cotton absent any leuco entity.

In one preferred embodiment, the laundry care composition after 30 daysof storage provides a whiteness benefit to cotton upon washing that isgreater than the initial whiteness benefit. In one embodiment, thelaundry care composition has a Whiteness Improvement Number (WIN_(x)),as described in further detail herein, of at least 5% after 1, 2, 4, 7,14, 21, 28, 30, 60, 90, 120, 150, 180, 270 or 360 days of storage at 25°C. or after 1, 2, 4, 7, 14, 21, 28, 30, 45 or 60 days storage at 50° C.In another embodiment, the laundry care composition has a WhitenessImprovement Number (WIN_(x)) of at least 10% after 1, 2, 4, 7, 14, 21,28, 30, 60, 90, 120, 150, 180, 270 or 360 days of storage at 25° C. orafter 1, 2, 4, 7, 14, 21, 28, 30, 45 or 60 days storage at 50° C. In oneembodiment, the laundry care composition has a Whiteness ImprovementNumber (WIN_(x)) of at least 5% after 14 days of storage at 25° C. and,most preferably, a Whiteness Improvement Number (WIN_(x)) of at least10% after 28 days of storage at 25° C. In another embodiment, thelaundry care composition has a Whiteness Improvement Number (WIN_(x)),as described in further detail herein, of at least 5% after 14 days ofstorage at 50° C. and, most preferably, a Whiteness Improvement Number(WIN_(x)) of at least 10% after 28 days of storage at 50° C.

Laundry Care Ingredients

Surfactant System

The products of the present invention may comprise from about 0.00 wt %,more typically from about 0.10 to 80% by weight of a surfactant. In oneaspect, such compositions may comprise from about 5% to 50% by weight ofsurfactant. Surfactants utilized can be of the anionic, nonionic,amphoteric, ampholytic, zwitterionic, or cationic type or can comprisecompatible mixtures of these types. Anionic and nonionic surfactants aretypically employed if the fabric care product is a laundry detergent. Onthe other hand, cationic surfactants are typically employed if thefabric care product is a fabric softener.Anionic Surfactant

Useful anionic surfactants can themselves be of several different types.For example, water-soluble salts of the higher fatty acids, i.e.,“soaps”, are useful anionic surfactants in the compositions herein. Thisincludes alkali metal soaps such as the sodium, potassium, ammonium, andalkylolammonium salts of higher fatty acids containing from about 8 toabout 24 carbon atoms, or even from about 12 to about 18 carbon atoms.Soaps can be made by direct saponification of fats and oils or by theneutralization of free fatty acids. Particularly useful are the sodiumand potassium salts of the mixtures of fatty acids derived from coconutoil and tallow, i.e., sodium or potassium tallow and coconut soap.

Preferred alkyl sulphates are C8-18 alkyl alkoxylated sulphates,preferably a C12-15 alkyl or hydroxyalkyl alkoxylated sulphates.Preferably the alkoxylating group is an ethoxylating group. Typicallythe alkyl alkoxylated sulphate has an average degree of alkoxylationfrom 0.5 to 30 or 20, or from 0.5 to 10. The alkyl group may be branchedor linear. The alkoxylated alkyl sulfate surfactant may be a mixture ofalkoxylated alkyl sulfates, the mixture having an average (arithmeticmean) carbon chain length within the range of about 12 to about 30carbon atoms, or an average carbon chain length of about 12 to about 15carbon atoms, and an average (arithmetic mean) degree of alkoxylation offrom about 1 mol to about 4 mols of ethylene oxide, propylene oxide, ormixtures thereof, or an average (arithmetic mean) degree of alkoxylationof about 1.8 mols of ethylene oxide, propylene oxide, or mixturesthereof. The alkoxylated alkyl sulfate surfactant may have a carbonchain length from about 10 carbon atoms to about 18 carbon atoms, and adegree of alkoxylation of from about 0.1 to about 6 mols of ethyleneoxide, propylene oxide, or mixtures thereof. The alkoxylated alkylsulfate may be alkoxylated with ethylene oxide, propylene oxide, ormixtures thereof. Alkyl ether sulfate surfactants may contain a peakedethoxylate distribution. Specific example include C12-C15 EO 2.5Sulfate, C14-C15 EO 2.5 Sulfate and C12-C15 EO 1.5 Sulfate derived fromNEODOL® alcohols from Shell and C12-C14 EO3 Sulfate, C12-C16 EO3Sulfate, C12-C14 EO2 Sulfate and C12-C14 EO1 Sulfate derived fromnatural alcohols from Huntsman. The AES may be linear, branched, orcombinations thereof. The alkyl group may be derived from synthetic ornatural alcohols such as those supplied by the tradename Neodol® byShell, Safol®, Lial®, and Isalchem® by Sasol or midcut alcohols derivedfrom vegetable oils such as coconut and palm kernel. Another suitableanionic detersive surfactant is alkyl ether carboxylate, comprising aC10-C26 linear or branched, preferably C10-C20 linear, most preferablyC16-C18 linear alkyl alcohol and from 2 to 20, preferably 7 to 13, morepreferably 8 to 12, most preferably 9.5 to 10.5 ethoxylates. The acidform or salt form, such as sodium or ammonium salt, may be used, and thealkyl chain may contain one cis or trans double bond. Alkyl ethercarboxylic acids are available from Kao (Akypo®), Huntsman (Empicol®)and Clariant (Emulsogen®).

Other useful anionic surfactants can include the alkali metal salts ofalkyl benzene sulfonates, in which the alkyl group contains from about 9to about 15 carbon atoms, in straight chain (linear) or branched chainconfiguration. In some examples, the alkyl group is linear. Such linearalkylbenzene sulfonates are known as “LAS.” In other examples, thelinear alkylbenzene sulfonate may have an average number of carbon atomsin the alkyl group of from about 11 to 14. In a specific example, thelinear straight chain alkylbenzene sulfonates may have an average numberof carbon atoms in the alkyl group of about 11.8 carbon atoms, which maybe abbreviated as C11.8 LAS. Preferred sulphonates are C10-13 alkylbenzene sulphonate. Suitable alkyl benzene sulphonate (LAS) may beobtained, by sulphonating commercially available linear alkyl benzene(LAB); suitable LAB includes low 2-phenyl LAB, such as those supplied bySasol under the tradename Isochem® or those supplied by Petresa underthe tradename Petrelab®, other suitable LAB include high 2-phenyl LAB,such as those supplied by Sasol under the tradename Hyblene®. A suitableanionic detersive surfactant is alkyl benzene sulphonate that isobtained by DETAL catalyzed process, although other synthesis routes,such as HF, may also be suitable. In one aspect a magnesium salt of LASis used. Suitable anionic sulfonate surfactants for use herein includewater-soluble salts of C8-C18 alkyl or hydroxyalkyl sulfonates; C11-C18alkyl benzene sulfonates (LAS), modified alkylbenzene sulfonate (MLAS)as discussed in WO 99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO99/05084, WO 99/05241, WO 99/07656, WO 00/23549, and WO 00/23548; methylester sulfonate (MES); and alpha-olefin sulfonate (AOS). Those alsoinclude the paraffin sulfonates may be monosulfonates and/ordisulfonates, obtained by sulfonating paraffins of 10 to 20 carbonatoms. The sulfonate surfactant may also include the alkyl glycerylsulfonate surfactants.

Anionic surfactants of the present invention may exist in an acid form,and said acid form may be neutralized to form a surfactant salt which isdesirable for use in the present detergent compositions. Typical agentsfor neutralization include the metal counterion base such as hydroxides,e.g., NaOH or KOH. Further preferred agents for neutralizing anionicsurfactants of the present invention and adjunct anionic surfactants orcosurfactants in their acid forms include ammonia, amines, oralkanolamines. Alkanolamines are preferred. Suitable non-limitingexamples including monoethanolamine, diethanolamine, triethanolamine,and other linear or branched alkanolamines known in the art; forexample, highly preferred alkanolamines include 2-amino-1-propanol,1-aminopropanol, monoisopropanolamine, or 1-amino-3-propanol.Nonionic Surfactant

Preferably the composition comprises a nonionic detersive surfactant.Suitable nonionic surfactants include alkoxylated fatty alcohols. Thenonionic surfactant may be selected from ethoxylated alcohols andethoxylated alkyl phenols of the formula R(OC2H4), OH, wherein R isselected from the group consisting of aliphatic hydrocarbon radicalscontaining from about 8 to about 15 carbon atoms and alkyl phenylradicals in which the alkyl groups contain from about 8 to about 12carbon atoms, and the average value of n is from about 5 to about 15.Other non-limiting examples of nonionic surfactants useful hereininclude: C8-C18 alkyl ethoxylates, such as, NEODOL® nonionic surfactantsfrom Shell; C6-C12 alkyl phenol alkoxylates where the alkoxylate unitsmay be ethyleneoxy units, propyleneoxy units, or a mixture thereof;C12-C18 alcohol and C6-C12 alkyl phenol condensates with ethyleneoxide/propylene oxide block polymers such as Pluronic® from BASF;C14-C22 mid-chain branched alcohols, BA; C14-C22 mid-chain branchedalkyl alkoxylates, BAEx, wherein x is from 1 to 30;alkylpolysaccharides; specifically alkylpolyglycosides; polyhydroxyfatty acid amides; and ether capped poly(oxyalkylated) alcoholsurfactants. Specific example include C12-C15 EO7 and C14-C15 EO7NEODOL® nonionic surfactants from Shell, C12-C14 EO7 and C12-C14 EO9Surfonic® nonionic surfactants from Huntsman.

Highly preferred nonionic surfactants are the condensation products ofGuerbet alcohols with from 2 to 18 moles, preferably 2 to 15, morepreferably 5-9 of ethylene oxide per mole of alcohol. Suitable nonionicsurfactants include those with the trade name Lutensol® from BASF.Lutensol XP-50 is a Guerbet ethoxylate that contains an average of about5 ethoxy groups. Lutensol XP-80 and containing an average of about 8ethoxy groups. Other suitable non-ionic surfactants for use hereininclude fatty alcohol polyglycol ethers, alkylpolyglucosides and fattyacid glucamides, alkylpolyglucosides based on Guerbet alcohols.

Amphoteric Surfactant

The surfactant system may include amphoteric surfactant, such as amineoxide. Preferred amine oxides are alkyl dimethyl amine oxide or alkylamido propyl dimethyl amine oxide, more preferably alkyl dimethyl amineoxide and especially coco dimethyl amino oxide Amine oxide may have alinear or mid-branched alkyl moiety.

Ampholytic Surfactants

The surfactant system may comprise an ampholytic surfactant. Specific,non-limiting examples of ampholytic surfactants include: aliphaticderivatives of secondary or tertiary amines, or aliphatic derivatives ofheterocyclic secondary and tertiary amines in which the aliphaticradical can be straight- or branched-chain. One of the aliphaticsubstituents may contain at least about 8 carbon atoms, for example fromabout 8 to about 18 carbon atoms, and at least one contains an anionicwater-solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S.Pat. No. 3,929,678 at column 19, lines 18-35, for suitable examples ofampholytic surfactants.

Zwitterionic Surfactant

Zwitterionic surfactants are known in the art, and generally includesurfactants which are neutrally charged overall, but carry at least onepositive charged atom/group and at least one negatively chargedatom/group. Examples of zwitterionic surfactants include: derivatives ofsecondary and tertiary amines, derivatives of heterocyclic secondary andtertiary amines, or derivatives of quaternary ammonium, quaternaryphosphonium or tertiary sulfonium compounds. See U.S. Pat. No. 3,929,678at column 19, line 38 through column 22, line 48, for examples ofzwitterionic surfactants; betaines, including alkyl dimethyl betaine andcocodimethyl amidopropyl betaine, C₈ to C₁₈ (for example from C₁₂ toC₁₈) amine oxides and sulfo and hydroxy betaines, such asN-alkyl-N,N-dimethylammino-1-propane sulfonate where the alkyl group canbe C₈ to C₁₈ and in certain embodiments from C₁₀ to C₁₄. A preferredzwitterionic surfactant for use in the present invention is thecocoamidopropyl betaine.

Cationic Surfactants

Examples of cationic surfactants include quaternary ammoniumsurfactants, which can have up to 26 carbon atoms specific. Additionalexamples include a) alkoxylate quaternary ammonium (AQA) surfactants asdiscussed in U.S. Pat. No. 6,136,769; b) dimethyl hydroxyethylquaternary ammonium as discussed in U.S. Pat. No. 6,004,922; c)polyamine cationic surfactants as discussed in WO 98/35002, WO 98/35003,WO 98/35004, WO 98/35005, and WO 98/35006, which is herein incorporatedby reference; d) cationic ester surfactants as discussed in U.S. Pat.Nos. 4,228,042, 4,239,660 4,260,529 and U.S. Pat. No. 6,022,844, whichis herein incorporated by reference; and e) amino surfactants asdiscussed in U.S. Pat. No. 6,221,825 and WO 00/47708, which is hereinincorporated by reference, and specifically amido propyldimethyl amine(APA). Useful cationic surfactants also include those described in U.S.Pat. No. 4,222,905, Cockrell, issued Sep. 16, 1980, and in U.S. Pat. No.4,239,659, Murphy, issued Dec. 16, 1980, both of which are alsoincorporated herein by reference. Quaternary ammonium compounds may bepresent in fabric enhancer compositions, such as fabric softeners, andcomprise quaternary ammonium cations that are positively chargedpolyatomic ions of the structure NR₄ ⁺, where R is an alkyl group or anaryl group.

Adjunct Cleaning Additives

The cleaning compositions of the invention may also contain adjunctcleaning additives. The precise nature of the cleaning adjunct additivesand levels of incorporation thereof will depend on the physical form ofthe cleaning composition, and the precise nature of the cleaningoperation for which it is to be used.

The adjunct cleaning additives may be selected from the group consistingof builders, structurants or thickeners, clay soilremoval/anti-redeposition agents, polymeric soil release agents,polymeric dispersing agents, polymeric grease cleaning agents, enzymes,enzyme stabilizing systems, bleaching compounds, bleaching agents,bleach activators, bleach catalysts, brighteners, dyes, hueing agents,dye transfer inhibiting agents, chelating agents, suds supressors,softeners, and perfumes. This listing of adjunct cleaning additives isexemplary only, and not by way of limitation of the types of adjunctcleaning additives which can be used. In principle, any adjunct cleaningadditive known in the art may be used in the instant invention.

Polymers

The composition may comprise one or more polymers. Non-limitingexamples, all of which may be optionally modified, includepolyethyleneimines, carboxymethylcellulose, poly(vinyl-pyrrolidone),poly (ethylene glycol), poly(vinyl alcohol),poly(vinylpyridine-N-oxide), poly(vinylimidazole), polycarboxylates oralkoxylated substituted phenols (ASP). as described in WO 2016/041676.An example of ASP dispersants, include but are not limited to, HOSTAPALBV CONC S1000 available from Clariant.

Polyamines may be used for grease, particulate removal or stain removal.A wide variety of amines and polyaklyeneimines can be alkoxylated tovarious degrees to achieve hydrophobic or hydrophilic cleaning. Suchcompounds may include, but are not limited to, ethoxylatedpolyethyleneimine, ethoxylated hexamethylene diamine, and sulfatedversions thereof. Useful examples of such polymers are HP20 availablefrom BASF or a polymer having the following general structure:

bis((C₂H₅O)(C₂H₄O)_(n))(CH₃)—N+—C_(x)H_(2x)—N+—(CH₃)-bis((C₂H₅O)(C₂H₄O)_(n),wherein n=from 20 to 30, and x=from 3 to 8, or sulphated or sulphonatedvariants thereof. Polypropoxylated-polyethoxylated amphiphilicpolyethyleneimine derivatives may also be included to achieve greatergrease removal and emulsification. These may comprise alkoxylatedpolyalkylenimines, preferably having an inner polyethylene oxide blockand an outer polypropylene oxide block. Detergent compositions may alsocontain unmodified polyethyleneimines useful for enhanced beverage stainremoval. PEI's of various molecular weights are commercially availablefrom the BASF Corporation under the trade name Lupasol® Examples ofsuitable PEI's include, but are not limited to, Lupasol FG®, LupasolG-35®.

The composition may comprise one or more carboxylate polymers, such as amaleate/acrylate random copolymer or polyacrylate homopolymer useful aspolymeric dispersing agents. Alkoxylated polycarboxylates such as thoseprepared from polyacrylates are also useful to provide clay dispersancy.Such materials are described in WO 91/08281. Chemically, these materialscomprise polyacrylates having one ethoxy side-chain per every 7-8acrylate units. The side-chains are of the formula —(CH₂CH₂O)_(m)(CH₂)_(n)CH₃ wherein m is 2-3 and n is 6-12. The side-chains are esteror ether-linked to the polyacrylate “backbone” to provide a “comb”polymer type structure.

Preferred amphiphilic graft co-polymer(s) comprise (i) polyethyeleneglycol backbone; and (ii) at least one pendant moiety selected frompolyvinyl acetate, polyvinyl alcohol and mixtures thereof. An example ofan amphiphilic graft co-polymer is Sokalan HP22, supplied from BASF.

Alkoxylated substituted phenols as described in WO 2016/041676 are alsosuitable examples of polymers that provide clay dispersancy. Hostapal BVConc 51000, available from Clariant, is one non-limiting example of anASP dispersant.

Preferably the composition comprises one or more soil release polymers.Suitable soil release polymers are polyester soil release polymers suchas Repel-o-tex polymers, including Repel-o-tex SF, SF-2 and SRP6supplied by Rhodia. Other suitable soil release polymers include Texcarepolymers, including Texcare SRA100, SRA300, SRN100, SRN170, SRN240,SRN260 SRN300 and SRN325 supplied by Clariant. Other suitable soilrelease polymers are Marloquest polymers, such as Marloquest SL, HSCB,L235M, B, G82 supplied by Sasol. Other suitable soil release polymersinclude methyl-capped ethoxylated propoxylated soil release polymers asdescribed in U.S. Pat. No. 9,365,806.

Preferably the composition comprises one or more polysaccharides whichmay in particular be chosen from carboxymethyl cellulose,methylcarboxymethylcellulose, sulfoethylcellulose,methylhydroxyethylcellulose, carboxymethyl xylogluc an, carboxymethylxylan, sulfoethylgalactomannan, carboxymethyl galactomannan, hydoxyethylgalactomannan, sulfoethyl starch, carboxymethyl starch, and mixturethereof. Other polysaccharides suitable for use in the present inventionare the glucans. Preferred glucans are Poly alpha-1,3-glucan which is apolymer comprising glucose monomeric units linked together by glycosidiclinkages (i.e., glucosidic linkages), wherein at least about 50% of theglycosidic linkages are alpha-1,3-glycosidic linkages. Polyalpha-1,3-glucan is a type of polysaccharide. Poly alpha-1,3-glucan canbe enzymatically produced from sucrose using one or moreglucosyltransferase enzymes, such as described in U.S. Pat. No.7,000,000, and U.S. Patent Appl. Publ. Nos. 2013/0244288 and2013/0244287 (all of which are incorporated herein by reference), forexample.

Other suitable polysaccharides for use in the composition are cationicpolysaccharides. Examples of cationic polysaccharides include cationicguar gum derivatives, quaternary nitrogen-containing cellulose ethers,and synthetic polymers that are copolymers of etherified cellulose, guarand starch. When used, the cationic polymers herein are either solublein the composition or are soluble in a complex coacervate phase in thecomposition formed by the cationic polymer and the anionic, amphotericand/or zwitterionic surfactant component described hereinbefore.Suitable cationic polymers are described in U.S. Pat. Nos. 3,962,418;3,958,581; and U.S. Publication No. 2007/0207109A1.

Polymers can also function as deposition aids for other detergent rawmaterials. Preferred deposition aids are selected from the groupconsisting of cationic and nonionic polymers. Suitable polymers includecationic starches, cationic hydroxyethylcellulose,polyvinylformaldehyde, locust bean gum, mannans, xyloglucans, tamarindgum, polyethyleneterephthalate and polymers containingdimethylaminoethyl methacrylate, optionally with one or more monomersselected from the group comprising acrylic acid and acrylamide.

Additional Amines

Polyamines are known to improve grease removal. Preferred cyclic andlinear amines for performance are 1,3-bis (methylamine)-cyclohexane,4-methylcyclohexane-1,3-diamine (Baxxodur ECX 210 supplied by BASF) 1,3propane diamine, 1,6 hexane diamine, 1,3 pentane diamine (Dytek EPsupplied by Invista), 2-methyl 1,5 pentane diamine (Dytek A supplied byInvista). U.S. Pat. No. 6,710,023 discloses hand dishwashingcompositions containing said diamines and polyamines containing at least3 protonable amines Polyamines according to the invention have at leastone pka above the wash pH and at least two pka's greater than about 6and below the wash pH. Preferred polyamines with are selected from thegroup consisting of tetraethylenepentamine, hexaethylhexamine,heptaethylheptamines, octaethyloctamines, nonethylnonamines, andmixtures thereof commercially available from Dow, BASF and Huntman.Especially preferred polyetheramines are lipophilic modified asdescribed in U.S. Pat. Nos. 9,752,101, 9,487,739, 9,631,163.

Dye Transfer Inhibitor (DTI)

The composition may comprise one or more dye transfer inhibiting agents.In one embodiment of the invention the inventors have surprisingly foundthat compositions comprising polymeric dye transfer inhibiting agents inaddition to the specified dye give improved performance. This issurprising because these polymers prevent dye deposition. Suitable dyetransfer inhibitors include, but are not limited to,polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers ofN-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones andpolyvinylimidazoles or mixtures thereof. Suitable examples includePVP-K15, PVP-K30, ChromaBond S-400, ChromaBond S-403E and ChromabondS-100 from Ashland Aqualon, and Sokalan HP165, Sokalan HP50, SokalanHP53, Sokalan HP59, Sokalan® HP 56K, Sokalan® HP 66 from BASF. Othersuitable DTIs are as described in WO2012/004134. When present in asubject composition, the dye transfer inhibiting agents may be presentat levels from about 0.0001% to about 10%, from about 0.01% to about 5%or even from about 0.1% to about 3% by weight of the composition.

Enzymes

Enzymes may be included in the cleaning compositions for a variety ofpurposes, including removal of protein-based, carbohydrate-based, ortriglyceride-based stains from substrates, for the prevention of refugeedye transfer in fabric laundering, and for fabric restoration. Suitableenzymes include proteases, amylases, lipases, carbohydrases, cellulases,oxidases, peroxidases, mannanases, and mixtures thereof of any suitableorigin, such as vegetable, animal, bacterial, fungal, and yeast origin.Other enzymes that may be used in the cleaning compositions describedherein include hemicellulases, peroxidases, proteases, cellulases,endoglucanases, xylanases, lipases, phospholipases, amylases,gluco-amylases, xylanases, esterases, cutinases, pectinases,keratanases, reductases, oxidases, phenoloxidases, lipoxygenases,ligninases, pullulanases, tannases, pentosanases, malanases,β-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases,or mixtures thereof, esterases, mannanases, pectate lyases, and ormixtures thereof. Other suitable enzymes include Nuclease enzyme. Thecomposition may comprise a nuclease enzyme. The nuclease enzyme is anenzyme capable of cleaving the phosphodiester bonds between thenucleotide sub-units of nucleic acids. The nuclease enzyme herein ispreferably a deoxyribonuclease or ribonuclease enzyme or a functionalfragment thereof. Enzyme selection is influenced by factors such aspH-activity and/or stability optima, thermostability, and stability toactive detergents, builders, and the like.

The enzymes may be incorporated into the cleaning composition at levelsfrom 0.0001% to 5% of active enzyme by weight of the cleaningcomposition. The enzymes can be added as a separate single ingredient oras mixtures of two or more enzymes.

In some embodiments, lipase may be used. Lipase may be purchased underthe trade name Lipex from Novozymes (Denmark). Amylases (Natalase®,Stainzyme®, Stainzyme Plus®) may be supplied by Novozymes, Bagsvaerd,Denmark. Proteases may be supplied by Genencor International, Palo Alto,Calif., USA (e.g. Purafect Prime®) or by Novozymes, Bagsvaerd, Denmark(e.g. Liquanase®, Coronase®, Savinase®). Other preferred enzymes includepectate lyases preferably those sold under the trade names Pectawash®,Xpect®, Pectaway® and the mannanases sold under the trade namesMannaway® (all from Novozymes A/S, Bagsvaerd, Denmark), and Purabrite®(Genencor International Inc., Palo Alto, Calif.). A range of enzymematerials and means for their incorporation into synthetic cleaningcompositions is disclosed in WO 9307263 A; WO 9307260 A; WO 8908694 A;U.S. Pat. Nos. 3,553,139; 4,101,457; and U.S. Pat. No. 4,507,219. Enzymematerials useful for liquid cleaning compositions, and theirincorporation into such compositions, are disclosed in U.S. Pat. No.4,261,868.

Enzyme Stabilizing System

The enzyme-containing compositions described herein may optionallycomprise from about 0.001% to about 10%, in some examples from about0.005% to about 8%, and in other examples, from about 0.01% to about 6%,by weight of the composition, of an enzyme stabilizing system. Theenzyme stabilizing system can be any stabilizing system which iscompatible with the detersive enzyme. Such a system may be inherentlyprovided by other formulation actives, or be added separately, e.g., bythe formulator or by a manufacturer of detergent-ready enzymes. Suchstabilizing systems can, for example, comprise calcium ion, boric acid,propylene glycol, short chain carboxylic acids, boronic acids, chlorinebleach scavengers and mixtures thereof, and are designed to addressdifferent stabilization problems depending on the type and physical formof the cleaning composition. See U.S. Pat. No. 4,537,706 for a review ofborate stabilizers.

Chelating Agent.

Preferably the composition comprises chelating agents and/or crystalgrowth inhibitor. Suitable molecules include copper, iron and/ormanganese chelating agents and mixtures thereof. Suitable moleculesinclude aminocarboxylates, aminophosphonates, succinates, salts thereof,and mixtures thereof. Non-limiting examples of suitable chelants for useherein include ethylenediaminetetracetates,N-(hydroxyethyl)-ethylene-diamine-triacetates, nitrilotriacetates,ethylenediamine tetraproprionates, triethylene-tetraamine-hexacetates,diethylenetriamine-pentaacetates, ethanoldiglycines,ethylenediaminetetrakis (methylenephosphonates), diethylenetriaminepenta(methylene phosphonic acid) (DTPMP), ethylenediamine disuccinate(EDDS), hydroxyethanedimethylenephosphonic acid (HEDP),methylglycinediacetic acid (MGDA), diethylenetriaminepentaacetic acid(DTPA), and 1,2-diydroxybenzene-3,5-disulfonic acid (Tiron), saltsthereof, and mixtures thereof. Tiron as well as other sulphonatedcatechols may also be used as effective heavy metal chelants. Othernon-limiting examples of chelants of use in the present invention arefound in U.S. Pat. Nos. 7,445,644, 7,585,376 and 2009/0176684A1. Othersuitable chelating agents for use herein are the commercial DEQUESTseries, and chelants from Monsanto, DuPont, and Nalco Inc.

Brighteners

Optical brighteners or other brightening or whitening agents may beincorporated at levels of from about 0.01% to about 1.2%, by weight ofthe composition, into the cleaning compositions described herein.Commercial optical brighteners, which may be used herein, can beclassified into subgroups, which include, but are not necessarilylimited to, derivatives of stilbene, pyrazoline, coumarin, carboxylicacid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and6-membered-ring heterocycles, and other miscellaneous agents. Examplesof such brighteners are disclosed in “The Production and Application ofFluorescent Brightening Agents,” M. Zahradnik, John Wiley & Sons, NewYork (1982). Specific, non-limiting examples of optical brightenerswhich may be useful in the present compositions are those identified inU.S. Pat. Nos. 4,790,856 and 3,646,015. Highly preferred Brightenersinclude Disodium4,4′-bis{[4-anilino-6-[bis(2-hydroxyethyl)amino-s-triazin-2-yl]-amino}-2,2′-stilbenedisulfonate,4,4′-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2′-stilbenedisulfonate,Disodium4,4″-bis[(4,6-di-anilino-s-triazin-2-yl)-amino]-2,2′-stilbenedisulfonateand disodium 4,4′-bis-(2-sulfostyryl)biphenyl.

Bleaching Agents.

It may be preferred for the composition to comprise one or morebleaching agents. Suitable bleaching agents include photobleaches,hydrogen peroxide, sources of hydrogen peroxide, pre-formed peracids andmixtures thereof.

(1) photobleaches for example sulfonated zinc phthalocyanine sulfonatedaluminium phthalocyanines, xanthene dyes and mixtures thereof;

(2) pre-formed peracids: Suitable preformed peracids include, but arenot limited to compounds selected from the group consisting ofpre-formed peroxyacids or salts thereof typically a percarboxylic acidsand salts, percarbonic acids and salts, perimidic acids and salts,peroxymonosulfuric acids and salts, for example, Oxone®, and mixturesthereof. Suitable examples include peroxycarboxylic acids or saltsthereof, or peroxysulphonic acids or salts thereof. Particularlypreferred peroxyacids are phthalimido-peroxy-alkanoic acids, inparticular ε-phthalimido peroxy hexanoic acid (PAP). Preferably, theperoxyacid or salt thereof has a melting point in the range of from 30°C. to 60° C.

(3) sources of hydrogen peroxide, for example, inorganic perhydratesalts, including alkali metal salts such as sodium salts of perborate(usually mono- or tetra-hydrate), percarbonate, persulphate,perphosphate, persilicate salts and mixtures thereof.

Fabric Shading Dyes

The fabric shading dye (sometimes referred to as hueing, bluing orwhitening agents) typically provides a blue or violet shade to fabric.Such dye(s) are well known in the art and may be used either alone or incombination to create a specific shade of hueing and/or to shadedifferent fabric types. The fabric shading dye may be selected from anychemical class of dye as known in the art, including but not limited toacridine, anthraquinone (including polycyclic quinones), azine, azo(e.g., monoazo, disazo, trisazo, tetrakisazo, polyazo), benzodifurane,benzodifuranone, carotenoid, coumarin, cyanine, diazahemicyanine,diphenylmethane, formazan, hemicyanine, indigoids, methane,naphthalimides, naphthoquinone, nitro, nitroso, oxazine, phthalocyanine,pyrazoles, stilbene, styryl, triarylmethane, triphenylmethane, xanthenesand mixtures thereof. The amount of adjunct fabric shading dye presentin a laundry care composition of the invention is typically from 0.0001to 0.05 wt % based on the total cleaning composition, preferably from0.0001 to 0.005 wt %. Based on the wash liquor, the concentration offabric shading dye typically is from 1 ppb to 5 ppm, preferably from 10ppb to 500 ppb.

Suitable fabric shading dyes include small molecule dyes, polymeric dyesand dye-clay conjugates. Preferred fabric shading dyes are selected fromsmall molecule dyes and polymeric dyes. Suitable small molecule dyes maybe selected from the group consisting of dyes falling into the ColourIndex (C.I., Society of Dyers and Colourists, Bradford, UK)classifications of Acid, Direct, Basic, Reactive, Solvent or Dispersedyes.

Suitable polymeric dyes include dyes selected from the group consistingof polymers containing covalently bound (sometimes referred to asconjugated) chromogens, (also known as dye-polymer conjugates), forexample polymers with chromogen monomers co-polymerized into thebackbone of the polymer and mixtures thereof. Preferred polymeric dyescomprise the optionally substituted alkoxylated dyes, such asalkoxylated triphenyl-methane polymeric colourants, alkoxylatedcarbocyclic and alkoxylated heterocyclic azo colourants includingalkoxylated thiophene polymeric colourants, and mixtures thereof, suchas the fabric-substantive colorants sold under the name of Liquitint®(Milliken, Spartanburg, S.C., USA).

Suitable dye clay conjugates include dye clay conjugates selected fromthe group comprising at least one cationic/basic dye and a smectiteclay; a preferred clay may be selected from the group consisting ofMontmorillonite clay, Hectorite clay, Saponite clay and mixturesthereof.

Pigments are well known in the art and may also be used in the laundrycare compositions herein. Suitable pigments include C.I Pigment Blues 15to 20, especially 15 and/or 16, C.I. Pigment Blue 29, C.I. PigmentViolet 15, Monastral Blue and mixtures thereof.

Builders

The cleaning compositions of the present invention may optionallycomprise a builder.

Builders selected from aluminosilicates and silicates assist incontrolling mineral hardness in wash water, or to assist in the removalof particulate soils from surfaces. Suitable builders may be selectedfrom the group consisting of phosphates polyphosphates, especiallysodium salts thereof; carbonates, bicarbonates, sesquicarbonates, andcarbonate minerals other than sodium carbonate or sesquicarbonate;organic mono-, di-, tri-, and tetracarboxylates, especiallywater-soluble non-surfactant carboxylates in acid, sodium, potassium oralkanolammonium salt form, as well as oligomeric or water-soluble lowmolecular weight polymer carboxylates including aliphatic and aromatictypes; and phytic acid. These may be complemented by borates, e.g., forpH-buffering purposes, or by sulfates, especially sodium sulfate and anyother fillers or carriers which may be important to the engineering ofstable surfactant and/or builder-containing cleaning compositions.pH Buffer System

The compositions may also include a pH buffer system. The cleaningcompositions herein may be formulated such that, during use in aqueouscleaning operations, the wash water will have a pH of between about 6.0and about 12, and in some examples, between about 7.0 and 11. Techniquesfor controlling pH at recommended usage levels include the use ofbuffers, alkalis, or acids, and are well known to those skilled in theart. These include, but are not limited to, the use of sodium carbonate,citric acid or sodium citrate, monoethanol amine or other amines, boricacid or borates, and other pH-adjusting compounds well known in the art.The cleaning compositions herein may comprise dynamic in-wash pHprofiles by delaying the release of citric acid.

Structurant/Thickeners

Structured liquids can either be internally structured, whereby thestructure is formed by primary ingredients (e.g. surfactant material)and/or externally structured by providing a three dimensional matrixstructure using secondary ingredients (e.g. polymers, clay and/orsilicate material). The composition may comprise from about 0.01% toabout 5%, by weight of the composition, of a structurant, and in someexamples, from about 0.1% to about 2.0%, by weight of the composition,of a structurant. The structurant may be selected from the groupconsisting of diglycerides and triglycerides, ethylene glycoldistearate, microcrystalline cellulose, cellulose-based materials,microfiber cellulose, biopolymers, xanthan gum, gellan gum, and mixturesthereof. In some examples, a suitable structurant includes hydrogenatedcastor oil, and non-ethoxylated derivatives thereof. Other suitablestructurants are disclosed in U.S. Pat. No. 6,855,680. Such structurantshave a thread-like structuring system having a range of aspect ratios.Further suitable structurants and the processes for making them aredescribed in WO 2010/034736.

Suds Suppressors

Compounds for reducing or suppressing the formation of suds can beincorporated into the cleaning compositions described herein. Sudssuppression can be of particular importance in the so-called “highconcentration cleaning process” as described in U.S. Pat. Nos.4,489,455, 4,489,574, and in front-loading style washing machines.

A wide variety of materials may be used as suds suppressors, and sudssuppressors are well known to those skilled in the art. See, forexample, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition,Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). Examples ofsuds suppressors include monocarboxylic fatty acid, and soluble saltstherein, high molecular weight hydrocarbons such as paraffin, fatty acidesters (e.g., fatty acid triglycerides), fatty acid esters of monovalentalcohols, aliphatic C18-C40 ketones (e.g., stearone), N-alkylated aminotriazines, waxy hydrocarbons preferably having a melting point belowabout 100° C., silicone suds suppressors, and secondary alcohols. Sudssuppressors are described in U.S. Pat. Nos. 2,954,347; 4,075,118;4,265,779; 4,265,779; 3,455,839; 3,933,672; 4,652,392; 4,978,471;4,983,316; 5,288,431; 4,639,489; 4,749,740; and 4,798,679.

The cleaning compositions herein may comprise from 0% to about 10%, byweight of the composition, of suds suppressor. When utilized as sudssuppressors, monocarboxylic fatty acids, and salts thereof, may bepresent in amounts up to about 5% by weight of the cleaning composition,and in some examples, may be from about 0.5% to about 3% by weight ofthe cleaning composition. Silicone suds suppressors may be utilized inamounts up to about 2.0% by weight of the cleaning composition, althoughhigher amounts may be used. Monostearyl phosphate suds suppressors maybe utilized in amounts ranging from about 0.1% to about 2% by weight ofthe cleaning composition. Hydrocarbon suds suppressors may be utilizedin amounts ranging from about 0.01% to about 5.0% by weight of thecleaning composition, although higher levels can be used. Alcohol sudssuppressors may be used at about 0.2% to about 3% by weight of thecleaning composition.

Suds Boosters

If high sudsing is desired, suds boosters such as the C10-C16alkanolamides may be incorporated into the cleaning compositions fromabout 1% to about 10% by weight of the cleaning composition. Someexamples include the C10-C14 monoethanol and diethanol amides. Ifdesired, water-soluble magnesium and/or calcium salts such as MgCl₂,MgSO₄, CaCl₂, CaSO₄, and the like, may be added at levels of about 0.1%to about 2% by weight of the cleaning composition, to provide additionalsuds and to enhance grease removal performance.

Fillers and Carriers

Fillers and carriers may be used in the cleaning compositions describedherein. As used herein, the terms “filler” and “carrier” have the samemeaning and can be used interchangeably. Liquid cleaning compositions,and other forms of cleaning compositions that include a liquid component(such as liquid-containing unit dose cleaning compositions), may containwater and other solvents as fillers or carriers. Low molecular weightprimary or secondary alcohols exemplified by methanol, ethanol,propanol, isopropanol, and phenoxyethanol are suitable. Monohydricalcohols may be used in some examples for solubilizing surfactants, andpolyols such as those containing from 2 to about 6 carbon atoms and from2 to about 6 hydroxy groups (e.g., 1,2-propanediol, 1,3-propanediol,2,3-butanediol, ethylene glycol, and glycerine may be used).Amine-containing solvents may also be used.

Methods of Use

The present invention includes methods for whitening fabric. Compactfluid detergent compositions that are suitable for sale to consumers aresuited for use in laundry pretreatment applications, laundry cleaningapplications, and home care applications. Such methods include, but arenot limited to, the steps of contacting detergent compositions in neatform or diluted in wash liquor, with at least a portion of a fabricwhich may or may not be soiled and then optionally rinsing the fabric.The fabric material may be subjected to a washing step prior to theoptional rinsing step. Machine laundry methods may comprise treatingsoiled laundry with an aqueous wash solution in a washing machine havingdissolved or dispensed therein an effective amount of a machine laundrydetergent composition in accord with the invention. An “effectiveamount” of the detergent composition means from about 20 g to about 300g of product dissolved or dispersed in a wash solution of volume fromabout 5 L to about 65 L. The water temperatures may range from about 5°C. to about 100° C. The water to soiled material (e.g., fabric) ratiomay be from about 1:1 to about 30:1. The compositions may be employed atconcentrations of from about 500 ppm to about 15,000 ppm in solution. Inthe context of a fabric laundry composition, usage levels may also varydepending not only on the type and severity of the soils and stains, butalso on the wash water temperature, the volume of wash water, and thetype of washing machine (e.g., top-loading, front-loading, vertical-axisJapanese-type automatic washing machine).The detergent compositions herein may be used for laundering of fabricsat reduced wash temperatures. These methods of laundering fabriccomprise the steps of delivering a laundry detergent composition towater to form a wash liquor and adding a laundering fabric to said washliquor, wherein the wash liquor has a temperature of from about 0° C. toabout 20° C., or from about 0° C. to about 15° C., or from about 0° C.to about 9° C. The fabric may be contacted to the water prior to, orafter, or simultaneous with, contacting the laundry detergentcomposition with water. Another method includes contacting a nonwovensubstrate, which is impregnated with the detergent composition, with asoiled material. As used herein, “nonwoven substrate” can comprise anyconventionally fashioned nonwoven sheet or web having suitable basisweight, caliper (thickness), absorbency, and strength characteristics.Non-limiting examples of suitable commercially available nonwovensubstrates include those marketed under the trade names SONTARA® byDuPont and POLY WEB® by James River Corp.Hand washing/soak methods, and combined hand washing with semi-automaticwashing machines, are also included.Packaging for the Compositions

The cleaning compositions described herein can be packaged in anysuitable container including those constructed from paper, cardboard,plastic materials, and any suitable laminates. An optional packagingtype is described in European Application No. 94921505.7.

Multi-Compartment Pouch

The cleaning compositions described herein may also be packaged as amulti-compartment cleaning composition.

Other Adjunct Ingredients

A wide variety of other ingredients may be used in the cleaningcompositions herein, including, for example, other active ingredients,carriers, hydrotropes, processing aids, dyes or pigments, solvents forliquid formulations, solid or other liquid fillers, erythrosine,colliodal silica, waxes, probiotics, surfactin, aminocellulosicpolymers, Zinc Ricinoleate, perfume microcapsules, rhamnolipds,sophorolipids, glycopeptides, methyl ester ethoxylates, sulfonatedestolides, cleavable surfactants, biopolymers, silicones, modifiedsilicones, aminosilicones, deposition aids, hydrotropes (especiallycumene-sulfonate salts, toluene-sulfonate salts, xylene-sulfonate salts,and naphalene salts), PVA particle-encapsulated dyes or perfumes,pearlescent agents, effervescent agents, color change systems, siliconepolyurethanes, opacifiers, tablet disintegrants, biomass fillers,fast-dry silicones, glycol distearate, starch perfume encapsulates,emulsified oils including hydrocarbon oils, polyolefins, and fattyesters, bisphenol antioxidants, micro-fibrous cellulose structurants,properfumes, styrene/acrylate polymers, triazines, soaps, superoxidedismutase, benzophenone protease inhibitors, functionalized TiO2,dibutyl phosphate, silica perfume capsules, and other adjunctingredients, choline oxidase, triarylmethane blue and violet basic dyes,methine blue and violet basic dyes, anthraquinone blue and violet basicdyes, azo dyes basic blue 16, basic blue 65, basic blue 66 basic blue67, basic blue 71, basic blue 159, basic violet 19, basic violet 35,basic violet 38, basic violet 48, oxazine dyes, basic blue 3, basic blue75, basic blue 95, basic blue 122, basic blue 124, basic blue 141, Nileblue A and xanthene dye basic violet 10, an alkoxylated triphenylmethanepolymeric colorant; an alkoxylated thiopene polymeric colorant;thiazolium dye, mica, titanium dioxide coated mica, bismuth oxychloride,and other actives.

Anti-oxidant: The composition may optionally contain an anti-oxidantpresent in the composition from about 0.001 to about 2% by weight.Preferably the antioxidant is present at a concentration in the range0.01 to 0.08% by weight. Mixtures of anti-oxidants may be used.

One class of anti-oxidants used in the present invention is alkylatedphenols. Hindered phenolic compounds are a preferred type of alkylatedphenols having this formula. A preferred hindered phenolic compound ofthis type is 3,5-di-tert-butyl-4-hydroxytoluene (BHT).

Furthermore, the anti-oxidant used in the composition may be selectedfrom the group consisting of α-, β-, γ-, δ-tocopherol, ethoxyquin,2,2,4-trimethyl-1,2-dihydroquinoline, 2,6-di-tert-butyl hydroquinone,tert-butyl hydroxyanisole, lignosulphonic acid and salts thereof, andmixtures thereof.

The cleaning compositions described herein may also contain vitamins andamino acids such as: water soluble vitamins and their derivatives, watersoluble amino acids and their salts and/or derivatives, water insolubleamino acids viscosity modifiers, dyes, nonvolatile solvents or diluents(water soluble and insoluble), pearlescent aids, pediculocides, pHadjusting agents, preservatives, skin active agents, sunscreens, UVabsorbers, niacinamide, caffeine, and minoxidil.

The cleaning compositions of the present invention may also containpigment materials such as nitroso, monoazo, disazo, carotenoid,triphenyl methane, triaryl methane, xanthene, quinoline, oxazine, azine,anthraquinone, indigoid, thionindigoid, quinacridone, phthalocianine,botanical, and natural colors, including water soluble components suchas those having C.I. Names.

The cleaning compositions of the present invention may also containantimicrobial agents. Cationic active ingredients may include but arenot limited to n-alkyl dimethyl benzyl ammonium chloride, alkyl dimethylethyl benzyl ammonium chloride, dialkyl dimethyl quaternary ammoniumcompounds such as didecyl dimethyl ammonium chloride,N,N-didecyl-Nmethyl-poly(oxyethyl) ammonium propionate, dioctyl didecylammonium chloride, also including quaternary species such asbenzethonium chloride and quaternary ammonium compounds with inorganicor organic counter ions such as bromine, carbonate or other moietiesincluding dialkyl dimethyl ammonium carbonates, as well as antimicrobialamines such as Chlorhexidine Gluconate, PHMB (Polyhexamethylenebiguanide), salt of a biguanide, a substituted biguanide derivative, anorganic salt of a quaternary ammonium containing compound or aninorganic salt of a quaternary ammonium containing compound or mixturesthereof.

In one aspect, such method comprises the steps of optionally washingand/or rinsing said surface or fabric, contacting said surface or fabricwith any composition disclosed in this specification then optionallywashing and/or rinsing said surface or fabric is disclosed, with anoptional drying step.

Drying of such surfaces or fabrics may be accomplished by any one of thecommon means employed either in domestic or industrial settings. Thefabric may comprise any fabric capable of being laundered in normalconsumer or institutional use conditions, and the invention is suitablefor cellulosic substrates and in some aspects also suitable forsynthetic textiles such as polyester and nylon and for treatment ofmixed fabrics and/or fibers comprising synthetic and cellulosic fabricsand/or fibers. As examples of synthetic fabrics are polyester, nylon,these may be present in mixtures with cellulosic fibers, for example,polycotton fabrics. The solution typically has a pH of from 7 to 11,more usually 8 to 10.5. The compositions are typically employed atconcentrations from 500 ppm to 5,000 ppm in solution. The watertemperatures typically range from about 5° C. to about 90° C. The waterto fabric ratio is typically from about 1:1 to about 30:1.Test MethodsFabric swatches used in the test methods herein are obtained fromTestfabrics, Inc. West Pittston, Pa., and are 100% Cotton, Style 403(cut to 2″×2″) and/or Style 464 (cut to 4″×6″), and an unbrightenedmultifiber fabric, specifically Style 41 (5 cm×10 cm).All reflectance spectra and color measurements, including L*, a*, b*,K/S, and Whiteness Index (WI CIE) values on dry fabric swatches, aremade using one of four spectrophotometers: (1) a Konica-Minolta 3610dreflectance spectrophotometer (Konica Minolta Sensing Americas, Inc.,Ramsey, N.J., USA; D65 illumination, 10° observer, UV light excluded),(2) a LabScan XE reflectance spectrophotometer (HunterLabs, Reston, Va.;D65 illumination, 10° observer, UV light excluded), (3) a Color-Eye®7000A (GretagMacbeth, New Windsor, N.Y., USA; D65 light, UV excluded),or (4) a Color i7 spectrophotometer (X-rite, Inc., Grand Rapids, Mich.,USA; D65 light, UV excluded). Measurements are performed using twolayers of fabric, obtained by stacking smaller internal replicates(e.g., 2″×2″ Style 403) or folding of larger fabric swatches (e.g.,4″×6″ style 464).Where fabrics are irradiated, unless otherwise indicated, the specifiedfabrics post-dry are exposed to simulated sunlight with irradiance of0.77 W/m² @ 420 nm in an Atlas Xenon Fade-Ometer Ci3000+ (Atlas MaterialTesting Technology, Mount Prospect, Ill., USA) equipped with Type SBorosilicate inner (Part no. 20277300) and outer (Part no. 20279600)filters, set at 37° C. maximum cabinet temperature, 57° C. maximum blackpanel temperature (BPT black panel geometry), and 35% RH (relativehumidity). Unless otherwise indicated, irradiation is continuous overthe stated duration.I. Method for Determining Leuco Compound Efficiency from a Wash Solution

Cotton swatches (Style 403) are stripped prior to use by washing at 49°C. two times with heavy duty liquid laundry detergent nil brightener(1.55 g/L in aqueous solution). A concentrated stock solution of eachleuco polymer to be tested is prepared in a solvent selected fromethanol or 50:50 ethanol:water, preferably ethanol.

A base wash solution is prepared by dissolving heavy duty liquid laundrydetergent nil brightener (5.23 g/1.0 L) in deionized water. Fourstripped cotton swatches are weighed together and placed in a 250 mLErlenmeyer flask along with two 10 mm glass marbles. A total of threesuch flasks are prepared for each wash solution to be tested. The basewash solution is dosed with the leuco polymer stock to achieve a washsolution with the desired 2.0×10⁻⁶ N wash concentration of leucomoieties. (By way of example, a 1.0 ppm wash solution of a leuco polymerwith equivalent weight of 493.65 g/equivalent leuco moiety, or a 1.5 ppmwash solution of a leuco colorant with equivalent weight of 757.97g/equivalent leuco moiety, provides a wash solution that is 2.0×10⁻⁶ Nin leuco moeity.)

An aliquot of this wash solution sufficient to provide a 10.0:1.0liquor:fabric (w/w) ratio is placed into each of the three 250 mLErlenmeyer flasks. Each flask is dosed with a 1000 gpg stock hardnesssolution to achieve a final wash hardness of 6 gpg (3:1 Ca:Mg).

The flasks are placed on a Model 75 wrist action shaker (BurrellScientific, Inc., Pittsburgh, Pa.) and agitated at the maximum settingfor 12 minutes, after which the wash solution is removed by aspiration,a volume of rinse water (0 gpg) equivalent to the amount of washsolution used is added. Each flask is dosed with a 1000 gpg stockhardness solution to achieve a final rinse hardness of 6 gpg (3:1 Ca:Mg)before agitating 4 more minutes. The rinse is removed by aspiration andthe fabric swatches are spun dry (Mini Countertop Spin Dryer, TheLaundry Alternative Inc., Nashua, N.H.) for 1 minute, then placed in afood dehydrator set at 135° F. to dry in the dark for 2 hours.

A. Dark Conditions Post-Dry

L*, a*, b*, and Whiteness Index (WI CIE) values for the cotton fabricsare measured on the dry swatches 48 hours following the drying procedureusing a LabScan XE reflectance spectrophotometer. The L*, a*, and b*values of the 12 swatches generated for each leuco compound (threeflasks with four swatches each) are averaged and the leuco compoundefficiency (LCE) of each leuco compound is calculated using thefollowing equation:LCE=DE*=[(L* _(c) −L* _(s))²+(a* _(c) −a* _(s))²+(b* _(c) −b*_(s))²]^(1/2)wherein the subscripts c and s respectively refer to the control, i.e.,the fabric washed in detergent with no leuco polymer, and the sample,i.e., the fabric washed in detergent containing leuco polymer.

The WI CIE values of the 12 swatches generated for each wash solution(three flasks with four swatches each) are averaged and the change inwhiteness index on washing is calculated using the following equation:ΔWI=WI CIE (after wash)−WI CIE (before wash)

B. Light Conditions Post-Dry

Because consumer habits vary greatly throughout the world, the methodsused must allow for the possibility of measuring the benefits of leucocompounds across conditions. One such condition is the exposure to lightfollowing drying. Some leuco compounds will not exhibit as large abenefit under dark storage as under light storage, so each leucocompound must be tested under both sets of conditions to determine theoptimum benefit. Therefore Method I includes exposure of the driedfabrics to simulated sunlight for various increments of time beforemeasurements are taken, and the LCE value is set to the maximum valueobtained from the set of exposure times described below.

The specified cotton fabrics post-dry are exposed to simulated sunlightfor 15 min, 30 min, 45 min, 60 min, 75 min, 90 min, 120 min, and 240min. The L*, a*, b*, and Whiteness Index (WI CIE) values for the cottonfabrics are measured on the swatches after each exposure period using aLabScan XE reflectance spectrophotometer. The calculation of the LCE andthe ΔWI value at each exposure time point is as described in Method I.A.above, and the LCE value and the AWI value for the leuco compound areset to the maximum values obtained from the set of exposure timeslisted.

II. Method for Determining Relative Hue Angle (vs. Nil Leuco Compound)

The relative hue angle delivered by a leuco compound to cotton fabricstreated according to Method I described above is determined as follows.

a) The a* and b* values of the 12 swatches from each solution areaveraged and the following formulas used to determine Δa* and Δb*:Δa*=a* _(s) −a* _(c) and Δb*=b* _(s) −b* _(c)

-   -   wherein the subscripts c and s respectively refer to the fabric        washed in detergent with no leuco compound and the fabric washed        in detergent containing leuco compound.

b) If the absolute value of both Δa* and Δb*<0.25, no Relative Hue Angle(RHA) is calculated. If the absolute value of either Δa* or Δb* is≥0.25, the RHA is determined using one of the following formulas:RHA=A TAN 2(Δa*,Δb*) for Δb*≥0RHA=360+A TAN 2(Δa*,Δb*) for Δb*<0

A relative hue angle can be calculated for each time point where data iscollected in either the dark post-dry or light post-dry assessments. Anyof these points may be used to satisfy the requirements of a claim.

III. Method for Determining Change in Whiteness Index for a Laundry CareFormulation

Cotton swatches (Style 403) are stripped prior to use by washing at 49°C. two times with heavy duty liquid laundry detergent nil brightener(1.55 g/L in aqueous solution).

A base wash solution is prepared by dissolving the laundry careformulation (5.23 g/1.0 L) in deionized water. Four stripped cottonswatches are weighed together and placed in a 250 mL Erlenmeyer flaskalong with two 10 mm glass marbles. A total of three such flasks areprepared.

An aliquot of this wash solution sufficient to provide a 10.0:1.0liquor:fabric (w/w) ratio is placed into each of the three 250 mLErlenmeyer flasks. Each flask is dosed with a 1000 gpg stock hardnesssolution to achieve a final wash hardness of 6 gpg (3:1 Ca:Mg).

The flasks are placed on a Model 75 wrist action shaker (BurrellScientific, Inc., Pittsburgh, Pa.) and agitated at the maximum settingfor 12 minutes, after which the wash solution is removed by aspiration,a volume of rinse water (0 gpg) equivalent to the amount of washsolution used is added. Each flask is dosed with a 1000 gpg stockhardness solution to achieve a final rinse hardness of 6 gpg (3:1 Ca:Mg)before agitating 4 more minutes. The rinse is removed by aspiration andthe fabric swatches are spun dry (Mini Countertop Spin Dryer, TheLaundry Alternative Inc., Nashua, N.H.) for 1 minute, then placed in afood dehydrator set at 135° F. to dry in the dark for 2 hours.

L*, a*, b*, and Whiteness Index (WI CIE) values for the cotton fabricsare measured on the dry swatches, according to Method I.A. and/or I.B.above, using a LabScan XE reflectance spectrophotometer. The WI CIEvalues of the 12 swatches generated for the laundry care formulation(three flasks with four swatches each) are averaged and the change inwhiteness index on washing is calculated using the following equation:ΔWI=WI CIE (after wash)−WI CIE (before wash)IV. Method for Determining Whiteness Improvement Number (WIN_(x))

A. Storage at 25° C.

The Whiteness Improvement Number (WIN_(x)) of a laundry care formulationrepresents the change in whiteness improvement delivered by the laundrycare formulation when used to wash cotton fabric in a standard testbetween day 0 (the date of initial testing of the formulation) and day x(the date the second wash test is run) when the laundry care formulationis stored in the dark at 25° C. between day 0 and day x.

One set of cotton fabrics is washed on day 0 according to Method IIIabove to obtain the change in whiteness index on day 0 (ΔWI_(day 0)).The laundry care formulation is placed in storage in the dark at 25° C.until day x. A second set of cotton fabrics is washed on day x accordingto Method III above to obtain the change in whiteness index on day x(ΔWI_(day x)). The Whiteness Improvement Number after x days (WIN_(x))is calculated as:WIN_(x)=[(ΔWI_(day x)/ΔWI_(day 0))−1.0]×100%wherein the subscript x is the number of days the product is storedbetween running the two tests. Values for x suitable for assessing theWIN include values of 1, 2, 4, 7, 14, 21, 28, 30, 60, 90, 120, 150, 180,270 and 360 days under the specified conditions. If the WIN_(x) at anyone of these values satisfies the requirements of any claim notrequiring a specific value for x, the claim requirement is deemed tohave been met regardless of the values at any other point in time.

B. Storage at 50° C.

The Whiteness Improvement Number (WIN_(x)) of a laundry care formulationrepresents the change in whiteness improvement delivered by the laundrycare formulation when used to wash cotton fabric in a standard testbetween day 0 (the date of initial testing of the formulation) and day x(the date the second wash test is run when the laundry care formulationis stored in the dark at 50° C. between day 0 and day x.

One set of cotton fabrics is washed on day 0 according to Method IIIabove to obtain the change in whiteness index on day 0 (ΔWI_(day 0)).The laundry care formulation is placed in storage in the dark at 50° C.until day x. A second set of cotton fabrics is washed on day x accordingto Method III above to obtain the change in whiteness index on day x(ΔWI_(day x)) The Whiteness Improvement Number after x days (WIN_(x)) iscalculated as:WIN_(x)=[(ΔWI_(day x)/ΔWI_(day 0))−1.0]×100%wherein the subscript x is the number of days the product is storedbetween running the two tests. Values for x suitable for assessing theWIN include values of 1, 2, 4, 7, 14, 21, 28, 30, 45 and 60 days underthe specified conditions. If the WIN_(x) at any one of these valuessatisfies the requirements of any claim not requiring a specific valuefor x, the claim requirement is deemed to have been met regardless ofthe values at any other point in time.

In the event that the value of the ΔWI_(day 0) turns out to be 0.0, thepositive value of the standard deviation for the measurement of thatvalue in that test may be supplied as the value for the ΔWI_(day 0), sothat the WIN may be calculated (note the denominator (ΔWI_(day 0))cannot be zero or the value is undefined). This applies to Method IV.Aand B.

Example 1: Determination of Bias of Leuco Colarants for Increasing theWhiteness of Aged Garments Over Clean New Garments

The test was run with a series of leuco colorants A-F (see structuresbelow) according to Method I.A. as found herein for the stripped cottonfabric with the following exception: the leuco colorants were run usingequimolar concentrations of leuco colorant (2.02×10⁻⁶ M). The testprocedure was then rerun as described replacing the stripped cotton withswatches cut from a consumer sourced aged T-shirt fabric (St. VincentDePaul 4″×6″ T-shirt swatches, heavy dingy; purchased from J&RCoordinating Services, Cincinnati, Ohio, USA), where the swatches of theT-shirt had WI CIE values before washing between 39.0 and 46.0. Thechange in Whiteness Index for both the stripped cotton fabrics andconsumer sourced aged T-shirt fabric washed in a composition accordingto Method I.A. were calculated according to the following equation:ΔWI=WI CIE after wash−WI CIE before wash.The WI CIE values measured at 48 hours after dark drying were used forthe above calculation in each instance. The ΔWI values for the control(AATCC nil-leuco) and sample (AATCC with leuco) were used to calculatethe δΔWI CIE values according to the equation below:δΔWI CIE=ΔWI_(sample)−ΔWI_(control)Results:

δΔWI CIE Stripped Heavy Entry Leuco Colorant^(a) Cotton^(b) Dingy^(c)Bias^(d) A

1.86 17.68  9.51 B

1.21 14.23 11.8 C

0.33 16.36 — D

0.01 18.34 — E

0.66 14.87 22.5 F

0.27 15.05 — ^(a)Structure shown is representative. ^(b)100% cotton,Style #403, Test Fabrics, Inc., stripped. ^(c)100% cotton white T-shirtsourced from consumer (see above for detail). ^(d)Value calculated onlyif δΔWI CIE (48 h) on CW120 ≥ 0.50.

The data in the table above show that a wide variety of substitutionsmay be employed in the leuco colorant without losing the ability of theleuco colorant to maintain a strong bias for higher whiteness benefitson aged consumer garments over stripped cotton.

Example 2

AATCC heavy duty liquid detergent without optical brightener wasprepared with 0.01 wt % and 0.04 wt % of leuco colorant A. These samplesand a control sample of AATCC heavy duty liquid detergent withoutoptical brightener and without leuco colorant A were stored at 23° C.and 50° C. for 7 months. The samples stored at 50° C. represents anartificially aged sample relative to the ones stored at roomtemperature, due to the storage at higher temperatures. Storage atelevated temperatures is well known to the skilled artisan as atechnique to accelerate aging.

Washes were performed according to Method I.A. described above with thefollowing exceptions: (a) the four cotton swatches were replaced by fourmulti-fiber fabric swatches (MFF41, obtained from Testfabrics, Inc.),and (b) one external replicate was performed with four internalreplicates.

The WI CIE values of the four MFF41 swatches generated for the laundrycare formulations are averaged and the change in whiteness index onwashing is calculated using the following equation:ΔWI=WI CIE (after wash)−WI CIE (before wash)The ΔWI values for the control (AATCC nil-leuco) and samples (AATCC with0.01 wt % or 0.04 wt % leuco colorant A) were used to calculate the δΔWICIE values according to the equation below:δΔWI CIE=ΔWI_(sample)−ΔWI_(control)The values obtained from this testing are shown in the table below forthe cotton segment of the MFF41 swatches as measured 48 hours afterdrying.

δΔ WI CIE (at 48 hours) Wt % Leuco Colorant A Aged (23° C.) Aged (50°C.) 0.01 0.42 0.97 0.04 1.19 2.02The data indicates that the detergent that has been aged longer(accelerated aging at higher temperatures) provides an increased changein whiteness index over the sample stored at lower temperatures. Thedetergents of the instant invention surprisingly give larger increasesin the whiteness index the longer the detergent is stored.

FORMULATION EXAMPLES

The following are illustrative examples of cleaning compositionsaccording to the present disclosure and are not intended to be limiting.

Examples 1-7: Heavy Duty Liquid Laundry Detergent Compositions

1 2 3 4 5 6 7 Ingredients % weight AE_(1.8)S 6.77 5.16 1.36 1.30 — — —AE₃S — — — — 0.45 — — LAS 0.86 2.06 2.72 0.68 0.95 1.56 3.55 HSAS 1.852.63 1.02 — — — — AE9 6.32 9.85 10.20  7.92 AE8 35.45  AE7 8.40 12.44 C₁₂₋₁₄ dimethyl Amine Oxide 0.30 0.73 0.23 0.37 — — — C₁₂₋₁₈ Fatty Acid0.80 1.90 0.60 0.99 1.20 — 15.00  Citric Acid 2.50 3.96 1.88 1.98 0.902.50 0.60 Optical Brightener 1 1.00 0.80 0.10 0.30 0.05 0.50  0.001Optical Brightener 3  0.001 0.05 0.01 0.20 0.50 — 1.00 Sodium formate1.60 0.09 1.20 0.04 1.60 1.20 0.20 DTI 0.32 0.05 — 0.60 — 0.60 0.01Sodium hydroxide 2.30 3.80 1.70 1.90 1.70 2.50 2.30 Monoethanolamine1.40 1.49 1.00 0.70 — — — Diethylene glycol 5.50 — 4.10 — — — — Chelant1 0.15 0.15 0.11 0.07 0.50 0.11 0.80 4-formyl-phenylboronic acid — — — —0.05 0.02 0.01 Sodium tetraborate 1.43 1.50 1.10 0.75 — 1.07 — Ethanol1.54 1.77 1.15 0.89 — 3.00 7.00 Polymer 1 0.10 — — — — — 2.00 Polymer 20.30 0.33 0.23 0.17 — — — Polymer 3 — — — — — — 0.80 Polymer 4 0.80 0.810.60 0.40 1.00 1.00 — 1,2-Propanediol — 6.60 — 3.30 0.50 2.00 8.00Structurant 0.10 — — — — — 0.10 Perfume 1.60 1.10 1.00 0.80 0.90 1.501.60 Perfume encapsulate 0.10 0.05 0.01 0.02 0.10 0.05 0.10 Protease0.80 0.60 0.70 0.90 0.70 0.60 1.50 Mannanase 0.07 0.05  0.045 0.06 0.04 0.045 0.10 Amylase 1 0.30 — 0.30 0.10 — 0.40 0.10 Amylase 2 — 0.20 0.100.15 0.07 — 0.10 Xyloglucanase 0.20 0.10 — — 0.05 0.05 0.20 Lipase 0.400.20 0.30 0.10 0.20 — — Polishing enzyme — 0.04 — — —  0.004 — Nuclease0.05 — — — — —  0.003 Dispersin B — — — 0.05 0.03  0.001  0.001Liquitint ® V200 0.01 — — — — —  0.005 Leuco colorant 0.05  0.035 0.010.02  0.004  0.002  0.004 Dye control agent — 0.3  — 0.03 — 0.3  0.3 Water, dyes & minors Balance pH 8.2Based on total cleaning and/or treatment composition weight. Enzymelevels are reported as raw material.

Examples 8 to 18: Unit Dose Compositions

These examples provide various formulations for unit dose laundrydetergents. Compositions 8 to 12 comprise a single unit dosecompartment. The film used to encapsulate the compositions ispolyvinyl-alcohol-based film.

8 9 10 11 12 Ingredients % weight LAS 19.09 16.76 8.59 6.56 3.44 AE3S1.91 0.74 0.18 0.46 0.07 AE7 14.00 17.50 26.33 28.08 31.59 Citric Acid0.6 0.6 0.6 0.6 0.6 C12-15 Fatty Acid 14.8 14.8 14.8 14.8 14.8 Polymer 34.0 4.0 4.0 4.0 4.0 Chelant 2 1.2 1.2 1.2 1.2 1.2 Optical Brightener 10.20 0.25 0.01 0.01 0.50 Optical Brightener 2 0.20 — 0.25 0.03 0.01Optical Brightener 3 0.18 0.09 0.30 0.01 — DTI 0.10 — 0.20 — — Glycerol6.1 6.1 6.1 6.1 6.1 Monoethanol amine 8.0 8.0 8.0 8.0 8.0Tri-isopropanol amine — — 2.0 — — Tri-ethanol amine — 2.0 — — — Cumenesulfonate — — — — 2.0 Protease 0.80 0.60 0.07 1.00 1.50 Mannanase 0.070.05 0.05 0.10 0.01 Amylase 1 0.20 0.11 0.30 0.50 0.05 Amylase 2 0.110.20 0.10 — 0.50 Polishing enzyme 0.005 0.05 — — — Nuclease 0.— 0.05 — —0.005 Dispersin B 0.010 0.05 0.005 0.005 — Cyclohexyl dimethanol — — —2.0 — Leuco Colorant 0.06 0.03 0.10 0.02 0.04 Liquitint ® V200 — — 0.010.05 — Structurant 0.14 0.14 0.14 0.14 0.14 Perfume 1.9 1.9 1.9 1.9 1.9Dye control agent 0.1 0.3 0.2 0.5 0.3 Water and miscellaneous To 100% pH7.5-8.2Based on total cleaning and/or treatment composition weight. Enzymelevels are reported as raw material.In the following examples the unit dose has three compartments, butsimilar compositions can be made with two, four or five compartments.The film used to encapsulate the compartments is polyvinyl alcohol.

Base compositions 13 14 15 16 Ingredients % weight HLAS 26.82 16.35 7.503.34 AE7 17.88 16.35 22.50 30.06 Citric Acid 0.5 0.7 0.6 0.5 C12-15Fatty acid 16.4 6.0 11.0 13.0 Polymer 1 2.9 0.1 — — Polymer 3 1.1 5.12.5 4.2 Cationic cellulose polymer — — 0.3 0.5 Polymer 6 — 1.5 0.3 0.2Chelant 2 1.1 2.0 0.6 1.5 Optical Brightener 1 0.20 0.25 0.01 0.005Optical Brightener 3 0.18 0.09 0.30 0.005 DTI 0.1 — 0.05 — Glycerol 5.35.0 5.0 4.2 Monoethanolamine 10.0 8.1 8.4 7.6 Polyethylene glycol — —2.5 3.0 Potassium sulfite 0.2 0.3 0.5 0.7 Protease 0.80 0.60 0.40 0.80Amylase 1 0.20 0.20 0.200 0.30 Polishing enzyme — — 0.005 0.005 Nuclease0.05 — — — Dispersin B — 0.010 0.010 0.010 MgCl₂ 0.2 0.2 0.1 0.3Structurant 0.2 0.1 0.2 0.2 Acid Violet 50 0.04 0.03 0.05 0.03Perfume/encapsulates 0.10 0.30 0.01 0.05 Dye control agent 0.2 0.03 0.4— Solvents and misc. To 100% pH 7.0-8.2 Finishing compositions 17 18Compartment A B C A B C Volume of each compartment 40 ml 5 ml 5 ml 40 ml5 ml 5 ml Ingredients Active material in Wt. % Perfume 1.6 1.6 1.6 1.61.6 1.6 Liquitint V200 ™ 0 0.006 0 0 0.004 — Leuco colorant 0.02 0.04 —— TiO2 — — 0.1 — 0.1 Sodium Sulfite 0.4 0.4 0.4 0.1 0.3 0.3 Polymer 5 —2 — — Hydrogenated castor oil 0.14 0.14 0.14 0.14 0.14 0.14 BaseComposition 13, 14, 15 Add to 100% or 16Based on total cleaning and/or treatment composition weight, enzymelevels are reported as raw material.

-   AE1.8S is C₁₂₋₁₅ alkyl ethoxy (1.8) sulfate-   AE3S is C₁₂₋₁₅ alkyl ethoxy (3) sulfate-   AE7 is C₁₂₋₁₃ alcohol ethoxylate, with an average degree of    ethoxylation of 7-   AE8 is C₁₂₋₁₃ alcohol ethoxylate, with an average degree of    ethoxylation of 8-   AE9 is C₁₂₋₁₃ alcohol ethoxylate, with an average degree of    ethoxylation of 9-   Amylase 1 is Stainzyme®, 15 mg active/g, supplied by Novozymes-   Amylase 2 is Natalase®, 29 mg active/g, supplied by Novozymes-   Xyloglucanase is Whitezyme®, 20 mg active/g, supplied by Novozymes-   Chelant 1 is diethylene triamine pentaacetic acid-   Chelant 2 is 1-hydroxyethane 1,1-diphosphonic acid-   Dispersin B is a glycoside hydrolase, reported as 1000 mg active/g-   DTI is either poly(4-vinylpyridine-1-oxide) (such as Chromabond    S-403E®), or poly(1-vinylpyrrolidone-co-1-vinylimidazole) (such as    Sokalan HP56®).-   Dye control agent Dye control agent in accordance with the    invention, for example Suparex® O.IN (M1), Nylofixan® P (M2),    Nylofixan® PM (M3), or Nylofixan® HF (M4)-   HSAS is mid-branched alkyl sulfate as disclosed in U.S. Pat. Nos.    6,020,303 and 6,060,443-   LAS is linear alkylbenzenesulfonate having an average aliphatic    carbon chain length C₉-C₁₅ (HLAS is acid form).-   Leuco colorant Any suitable leuco colorant or mixtures thereof    according to the instant invention.-   Lipase is Lipex®, 18 mg active/g, supplied by Novozymes-   Liquitint® V200 is a thiophene azo dye provided by Milliken-   Mannanase is Mannaway®, 25 mg active/g, supplied by Novozymes-   Nuclease is a Phosphodiesterase SEQ ID NO 1, reported as 1000 mg    active/g-   Optical Brightener 1 is disodium    4,4′-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2′-stilbenedisulfonate-   Optical Brightener 2 is disodium 4,4′-bis-(2-sulfostyryl)biphenyl    (sodium salt)-   Optical Brightener 3 is Optiblanc SPL10® from 3V Sigma-   Perfume encapsulate is a coreshell melamine formaldehyde perfume    microcapsules.-   Polishing enzyme is Para-nitrobenzyl esterase, reported as 1000 mg    active/g

Polymer 1 isbis((C₂H₅O)(C₂H₄O)n)(CH₃)—N⁺—C_(x)H_(2x)—N⁺—(CH₃)-bis((C₂H₅O)(C₂H₄O)n),wherein n=20-30, x=3 to 8 or sulphated or sulfonated variants thereof

-   Polymer 2 is ethoxylated (EO₁₅) tetraethylene pentamine-   Polymer 3 is ethoxylated polyethylenimine-   Polymer 4 is ethoxylated hexamethylene diamine-   Polymer 5 is Acusol 305, provided by Rohm&Haas-   Polymer 6 is a polyethylene glycol polymer grafted with vinyl    acetate side chains, provided by BASF.-   Protease is Purafect Prime®, 40.6 mg active/g, supplied by DuPont-   Structurant is Hydrogenated Castor Oil

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross referenced or relatedpatent or application and any patent application or patent to which thisapplication claims priority or benefit thereof, is hereby incorporatedherein by reference in its entirety unless expressly excluded orotherwise limited. The citation of any document is not an admission thatit is prior art with respect to any invention disclosed or claimedherein or that it alone, or in any combination with any other referenceor references, teaches, suggests or discloses any such invention.Further, to the extent that any meaning or definition of a term in thisdocument conflicts with any meaning or definition of the same term in adocument incorporated by reference, the meaning or definition assignedto that term in this document shall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

We claim:
 1. A laundry care composition comprising: (a) at least onelaundry care ingredient and (b) a leuco composition, wherein the laundrycare composition has a Whiteness Improvement Number (WIN_(x)) of atleast 5% after 14 days of storage at 50° C.
 2. The laundry carecomposition of claim 1, wherein the laundry care composition has aWhiteness Improvement Number (WIN_(x)) of at least 10% after 28 days ofstorage at 50° C.
 3. The laundry care composition of claim 1, whereinthe leuco composition is selected from the group consisting of adiarylmethane leuco, a triarylmethane leuco, an oxazine leuco, athiazine leuco, a hydroquinone leuco, an arylaminophenol leuco andmixtures thereof.
 4. The laundry care composition of claim 1, whereinthe leuco composition is selected from one or more compounds selectedfrom the group consisting of:

(f) mixtures thereof; wherein the ratio of Formula I-V to its oxidizedform is at least 1:3; wherein each individual R_(o), R_(m) and R_(p)group on each of rings A, B and C is independently selected from thegroup consisting of hydrogen, deuterium and R⁵; wherein each R⁵ isindependently selected from the group consisting of halogens, nitro,alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substitutedalkaryl, —C(O)R¹, —C(O)OR¹, —C(O)O⁻, —C(O)NR¹R², —OC(O)R¹, —OC(O)OR¹,—OC(O)NR¹R², —S(O)₂R¹, —S(O)₂OR¹, —S(O)₂O⁻, —S(O)₂NR¹R², —NR¹C(O)R²,—NR¹C(O)OR², —NR¹C(O)SR², —NR¹C(O)NR²R³, —OR¹, —NR¹R², —P(O)₂R¹,—P(O)(OR¹)₂, —P(O)(OR¹)O⁻, and —P(O)(O⁻)₂; wherein at least one of theR_(o) and R_(m) groups on at least one of the three rings A, B or C ishydrogen; each R_(p) is independently selected from hydrogen, —OR¹ and—NR¹R²; wherein G is independently selected from the group consisting ofhydrogen, deuterium, C₁-C₁₆ alkoxide, phenoxide, bisphenoxide, nitrite,nitrile, alkyl amine, imidazole, arylamine, polyalkylene oxide, halides,alkylsulfide, aryl sulfide, and phosphine oxide; wherein R¹, R² and R³are independently selected from the group consisting of hydrogen, alkyl,substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl,and R⁴; R⁴ is a organic group composed of one or more organic monomerswith said monomer molecular weights ranging from 28 to 500; wherein eand f are independently integers from 0 to 4; wherein each R²⁰ and R²¹is independently selected from the group consisting of a halogen, anitro group, alkyl groups, substituted alkyl groups, —NC(O)OR¹,—NC(O)SR¹, —OR¹, and —NR¹R²; wherein each R²⁵ is independently selectedfrom the group consisting of a monosaccharide moiety, a disaccharidemoiety, an oligosaccharide moiety, a polysaccharide moiety, —C(O)R¹,—C(O)OR¹, —C(O)NR¹R²; wherein each R²² and R²³ is independently selectedfrom the group consisting of hydrogen, an alkyl group, and substitutedalkyl groups; wherein R³⁰ is positioned ortho or para to the bridgingamine moiety and is selected from the group consisting of —OR³⁸ and—NR³⁶R³⁷, wherein each R³⁶ and R³⁷ is independently selected from thegroup consisting of hydrogen, an alkyl group, a substituted alkyl group,an aryl group, a substituted aryl group, an acyl group, R⁴, —C(O)OR¹,—C(O)R¹, and —C(O)NR¹R²; wherein R³⁸ is selected from the groupconsisting of hydrogen, an acyl group, —C(O)OR¹, —C(O)R¹, and—C(O)NR¹R²; wherein g and h are independently integers from 0 to 4;wherein each R³¹ and R³² is independently selected from the groupconsisting of an alkyl group, a substituted alkyl group, an aryl group,a substituted aryl group, an alkaryl, substituted alkaryl, —C(O)R¹,—C(O)OR¹, —C(O)O⁻, —C(O)NR¹R², —OC(O)R¹, —OC(O)OR¹, —OC(O)NR¹R²,—S(O)₂R¹, —S(O)₂OR¹, —S(O)₂O⁻, —S(O)₂NR¹R², —NR¹C(O)R², —NR¹C(O)OR²,—NR¹C(O)SR², —NR¹C(O)NR²R³, —OR¹, —NR¹R², —P(O)₂R¹, —P(O)(OR¹)₂,—P(O)(OR¹)O⁻, and —P(O)(O⁻)₂; wherein —NR³⁴R³⁵ is positioned ortho orpara to the bridging amine moiety and R³⁴ and R³⁵ are independentlyselected from the group consisting of hydrogen, an alkyl, a substitutedalkyl, an aryl, a substituted aryl, an alkaryl, a substituted alkaryl,and R⁴; wherein R³³ is independently selected from the group consistingof hydrogen, —S(O)₂R¹, —C(O)N(H)R¹; —C(O)OR¹; and —C(O)R¹; wherein wheng is 2 to 4, any two adjacent R³¹ groups may combine to form a fusedring of five or more members wherein no more than two of the atoms inthe fused ring may be nitrogen atoms; wherein X⁴⁰ is selected from thegroup consisting of an oxygen atom, a sulfur atom, and NR⁴⁵; wherein R⁴⁵is independently selected from the group consisting of hydrogen,deuterium, an alkyl, a substituted alkyl, an aryl, a substituted aryl,an alkaryl, a substituted alkaryl, —S(O)₂OH, —S(O)₂O⁻, —C(O)OR¹,—C(O)R¹, and —C(O)NR¹R²; wherein R⁴⁰ and R⁴¹ are independently selectedfrom the group consisting of —OR¹ and —NR¹R²; wherein j and k areindependently integers from 0 to 3; wherein R⁴² and R⁴³ areindependently selected from the group consisting of an alkyl, asubstituted alkyl, an aryl, a substituted aryl, an alkaryl, asubstituted alkaryl, —S(O)₂R¹, —C(O)NR¹R², —NC(O)OR¹, —NC(O)SR¹,—C(O)OR¹, —C(O)R¹, —OR¹, —NR¹R²; wherein R⁴⁴ is —C(O)R¹, —C(O)NR¹R², and—C(O)OR¹; wherein any charge present in any of the compounds is balancedwith a suitable independently selected internal or external counterion.5. The laundry care composition of claim 4, wherein two R_(o) groups ondifferent A, B and C rings combine to form a fused ring of five or moremembers.
 6. The laundry care composition of claim 5, wherein the fusedring is six or more members and two R_(o) groups on different A, B and Crings combine to form an organic linker containing one or moreheteroatoms.
 7. The laundry care composition of claim 6, wherein twoR_(o) on different A, B and C rings combine to form a heteroatom bridgeselected from —O— and —S— to create a six member fused ring.
 8. Thelaundry care composition of claim 4, wherein either an R_(o) and R_(m)on the same ring or an R_(m) and R_(p) on the same ring combine to forma fused aliphatic ring or fused aromatic ring.
 9. The laundry carecomposition of claim 4, wherein all four of the R_(o) and R_(m) groupson at least one of the three rings A, B or C are hydrogen.
 10. Thelaundry care composition of claim 9, wherein all of the R_(o) and R_(m)groups on all three rings A, B or C are hydrogen.
 11. The laundry carecomposition of claim 4, wherein all three R_(p) are —NR¹R².
 12. Thelaundry care composition of claim 4, wherein G is deuterium.
 13. Thelaundry care composition of claim 4, wherein the leuco composition hasfraction [(deuterium)/(deuterium+hydrogen)] for G is at least 0.20. 14.The laundry care composition of claim 13, wherein the fraction[(deuterium)/(deuterium+hydrogen)] for G is at least 0.80.
 15. Thelaundry care composition of claim 4, wherein the organic group may besubstituted with one or more additional leuco colorant moietiesconforming to the structure of Formula I.
 16. The laundry carecomposition of claim 4, wherein R⁴ is selected from the group consistingof alkyleneoxy, oxoalkyleneoxy, oxoalkyleneamine, epichlorohydrin,quaternized epichlorohydrin, alkyleneamine, hydroxyalkylene,acyloxyalkylene, carboxyalkylene, carboalkoxyalkylene, and sugar. 17.The laundry care composition of claim 4, wherein the suitableindependently selected external counterions are selected from the groupconsisting of Na, K, Mg, Ca, iminium, ammonium, phosphonium, fluoride,chloride, bromide, iodide, perchlorate, hydrogen sulfate, sulfate,aminosulfate, nitrate, dihydrogen phosphate, hydrogen phosphate,phosphate, bicarbonate, carbonate, methosulfate, ethosulfate, cyanate,thiocyanate, tetrachiorozincate, borate, tetrafluoroborate, acetate,chloroacetate, cyanoacetate, hydroxyacetate, aminoacetate,methylaminoacetate, di- and tri-chloroacetate, 2-chloro-propionate,2-hydroxypropionate, glycolate, thioglycolate, thioacetate,phenoxyacetate, trimethylacetate, valerate, palmitate, acrylate,oxalate, malonate, crotonate, succinate, citrate,methylene-bis-thioglycolate, ethylene-bis-iminoacetate,nitrilotriacetate, fumarate, maleate, benzoate, methylbenzoate,chlorobenzoate, dichlorobenzoate, hydroxybenzoate, aminobenzoate,phthalate, terephthalate, indolylacetate, chlorobenzenesulfonate,benzenesulfonate, toluenesulfonate, biphenyl-sulfonate andchlorotoluenesulfonate.
 18. The laundry care composition of claim 1,wherein the laundry care ingredient is selected from the groupconsisting of surfactants, builders, chelating agents, dye transferinhibiting agents, dispersants, enzymes, enzyme stabilizers, catalyticmaterials, bleach activators, polymeric dispersing agents, clay soilremoval agents, anti-redeposition agents, brighteners, suds suppressors,dyes, perfume, perfume delivery systems, structurants, fabric softeners,carriers, hydrotropes, processing aids, pigments, antioxidants andmixtures thereof.
 19. A method for treating textile articles comprisingthe steps of: (a) providing the laundry care composition of claim 1; (b)adding the laundry care composition to a liquid medium; (c) placingtextile articles in the liquid medium; (d) optionally, rinsing thetextile; and (e) drying the textile articles.